Compositions for use in golf balls

ABSTRACT

A golf ball comprises a core, an outer cover layer, and, optionally, an intermediate layer disposed between the core and the outer cover layer. The outer cover layer may comprise a polyurethane or polyurea composition. At least one portion of the golf ball comprises a composition that enhances physical properties and/or performance characteristics (e.g., coefficient of restitution) of the golf ball. Preferably, the coefficient of restitution of the core is 0.8 or greater.

FIELD OF THE INVENTION

This invention relates generally to golf balls and, in particular, golfball portions (e.g., cores) formed of a polymer composition includingone or more functional additives.

BACKGROUND

Conventional golf balls can be divided into two general classes: solid(i.e., non-wound) and wound. Solid golf balls include one-piece,two-piece (i.e., solid core and a cover), and multi-layer (i.e., solidcore of one or more layers and/or a cover of one or more layers) golfballs. Wound golf balls typically include a solid, hollow, orfluid-filled center, surrounded by a tensioned elastomeric material, anda cover. Solid balls have traditionally been considered longer and moredurable than wound balls, but also lack a particular “feel” provided bythe wound construction.

By altering ball construction and composition, manufacturers can vary awide range of playing characteristics, such as compression, velocity,and spin, each of which can be optimized for various playing abilities.One golf ball component, in particular, that many manufacturers arecontinually looking to improve is the center or core. The core becomesthe “engine” of the golf ball when hit with a club head. Generally, golfball cores and/or centers are constructed with a polybutadiene-basedpolymer composition. Compositions of this type are constantly beingaltered in an effort to provide a higher coefficient of restitution(“CoR”) while at the same time resulting in a lower compression which,in turn, can lower the golf ball spin rate, provide better “feel,” orboth. This is a difficult task, however, given the physical limitationsof currently-available polymers. As such, there remains a need for noveland improved golf ball core compositions.

SUMMARY OF THE INVENTION

The present disclosure is directed to a golf ball comprising a core andat least one layer disposed about the core. The core is preferablysolid. At least one of the core or the layer comprises a compositionformed from a base polymer, a crosslink initiator, and at least oneadditive selected from the group consisting of boranes, borates,boronates, borinates, heterocylic compounds having at least one boronatom as a ring member, boron-containing organosulfides,sulfur-containing silicocompounds, salts of such additives, and metalsalts, organometallic salts, and non-metal salts of boron complexes. Theadditive may be present in an amount of 0.1 phr to 5 phr by weight ofthe base polymer. The composition may further comprise at least onecomponent chosen from metal salts of unsaturated acids having 3 to 8carbon atoms, fillers, fatty acids and salts thereof. The core and/orthe golf ball may have a coefficient of restitution of 0.8 or greater.Preferably, the additive enhances the coefficient of restitution of thecore and/or reduces the compression of the core.

Preferably, the additive is chosen from monoorgano-, diorgano-, andtriorgano-borane compounds of or containing BR₃, boric acids,sulfur-substituted borates, amine borate esters, boronic acids,diboronates, borinic acids, dioxaborolanes, dioxaborinanes, compoundshaving the structures of B(OR)₃, B(OR″)₃N, R′B(OR)₂, YR″B(OR)₂,Y′[R″B(OR)₂]₂), R′₂B(OR), and S_(y)[(R″)_(z)G]₂, metal and non-metalsalts of such additives, salts containing tetraorgano-borane anionsR₄B^(⊖), where R and R′ are the same or different monovalent radicalsselected from the group consisting of H and organic radicals having 40or less carbon atoms, optionally having one or more heteroatoms,optionally substituted with one or more electron-withdrawing groups; R″is the same or different divalent radicals selected from the groupconsisting of organic radicals having 20 or less carbon atoms,optionally having one or more heteroatoms, optionally substituted withone or more electron-withdrawing groups; Y is selected from the groupconsisting of thiocyano, epoxyl, glycidyl, epithio, vinyl, allyl, amine,and AZ groups where A is oxygen or sulfur atom, and Z is selected fromthe group consisting of H, metal cations, organometallic cations, andnon-metal organic cations; Y′ is a divalent radical of polysulfide S_(y)or polyselenium Se_(y); G is the same or different Si-contaningmonovalent radicals; x is a whole number of 0, 1, 2, or 3; y is aninteger of 1 to 8; and z is 0 or 1. More preferably, the additive has atleast one C—O—B linkage, the carbon in the linkage being a secondary ortertiary carbon. Besides the boron-containing additive, the compositionmay further comprise at least one amine-based compound.

The core may have a diameter of 1.5 inches or greater, preferably 1.53inches or greater. The core may have a compression of 50 to 90, or45-80, preferably 45-70. The core may comprise a center and an outercore layer. The at least one layer may be an outer cover layer having athickness of 0.05 inches or less and a flexural modulus of 2,000 psi to30,000 psi, preferably formed from a polyurethane or polyurea, or be anintermediate layer, no thicker than 0.05 inches, disposed between thecore and an outer cover layer.

Definitions

Any numeric references to amounts, unless otherwise specified, are “byweight.” The term “equivalent weight” is a calculated value based on therelative amounts of the various ingredients used in making the specifiedmaterial and is based on the solids of the specified material. Therelative amounts are those that result in the theoretical weight ingrams of the material, like a polymer, produced from the ingredients andgive a theoretical number of the particular functional group that ispresent in the resulting polymer.

The subscript letters such as m, n, x, y, and z used herein within thegeneric structures are understood by one of ordinary skill in the art asthe degree of polymerization (i.e., the number of consecutivelyrepeating units). In the case of molecularly uniform products, thesenumbers are commonly integers, if not zero. In the case of molecularlynon-uniform products, these numbers are averaged numbers not limited tointegers, if not zero, and are understood to be the average degree ofpolymerization.

As used herein, the term “polymer” refers to oligomers, adducts,homopolymers, random copolymers, pseudo-copolymers, statisticalcopolymers, alternating copolymers, periodic copolymer, bipolymers,terpolymers, quaterpolymers, other forms of copolymers, substitutedderivatives thereof, and combinations of two or more thereof. Thesepolymers can be linear, branched, block, graft, monodisperse,polydisperse, regular, irregular, tactic, isotactic, syndiotactic,stereoregular, atactic, stereoblock, single-strand, double-strand, star,comb, dendritic, and/or ionomeric.

As used herein, the term “telechelic” refers to polymers having at leasttwo terminal reactive end-groups and capable of entering into furtherpolymerization through these reactive end-groups. Reactive end-groupsdisclosed herein include, without limitation, amine groups, hydroxylgroups, isocyanate groups, carboxylic acid groups, thiol groups, andcombinations thereof.

As referred to herein, lower alkyls and lower alkoxies include C₁₋₅,preferably C₁₋₃, alkyls and alkoxies, such as methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, t-butyl, amyl, isoamyl, methoxy, ethoxy,isopropoxy, isobutoxy, t-butoxy.

As referred to herein, halogens include fluorine, chlorine, bromine, andiodine.

As referred to herein, linear or branched alkyls include methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, amyl, isoamyl,n-hexyl, 2-ethyl-n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl,isononyl, n-dodecyl.

As referred to herein, substituted alkyls include cyanoalkyl, haloalkyl,hydroxyalkyl, alkoxyalkyl, preferably C₂₋₆, e.g., β-cyanoethyl,β-chloroethyl, β-hydroxyethyl, β-methoxyethyl, β-ethoxyethyl.Cycloalkyls include cyclopentyl, cycloheptyl, cyclohexyl, and maycomprise one or more C₁₋₄ alkyls.

As referred to herein, aralkyls and alkaryls include methylbenzyl,phenethyl, phenisopropyl, benzyl, and may be ring-substituted, such aswith halogen, methyl, and/or methoxy, like p-methylbenzyl, o- orp-chlorobenzyl, o- or p-tolyl, xylyl, o-, m- or p-chlorophenyl, and o-or p-methoxyphenyl.

As referred to herein, heterocyclic radicals include pyrrolidinyl,piperidinyl, pipecolinyl, morpholinyl, thiomorpholinyl, piperazinyl(e.g., N-methylpiperazinyl).

As used herein, the term “derivatives” refers to various compoundschemically derivable from the parent compounds, typically sharing one ormore chemical properties and/or reactivities with the parent compounds.When applicable, the derivatives of the compounds disclosed hereininclude, without limitation, substitution derivatives having one or moresubstituents, anhydrides, dimers, oligomers, esters such as alkyl (e.g.,methyl, ethyl, linear or branched C₁₋₁₂ alkyls), cycloalkyl, and arylesters, amides, halides, oxides, sulfides, and salts having metalcations (e.g., Na, K, Zn, Ca, Co, Mg, Ni), organometallic cations, andnon-metal cations (e.g., quaternary ammonium, quaternary pyridinium,quaternary quinolinium, (organo)phosphonium, (organo)sulfonium,(organo)oxonium, (organo)iodonium, (organo)azonium).

Other than in the operating examples, or unless otherwise expresslyspecified, all of the numerical ranges, amounts, values and percentagessuch as those for amounts of materials, times and temperatures ofreaction, ratios of amounts, values for molecular weight (whether numberaverage molecular weight (“M_(n)”) or weight average molecular weight(“M_(w)”), and others in the following portion of the specification maybe read as if prefaced by the word “about” even though the term “about”may not expressly appear with the value, amount or range. Accordingly,unless indicated to the contrary, the numerical parameters set forth inthe following specification and attached claims are approximations thatmay vary depending upon the desired properties sought to be obtained bythe present disclosure. At the very least, and not as an attempt tolimit the application of the doctrine of equivalents to the scope of theclaims, each numerical parameter should at least be construed in lightof the number of reported significant digits and by applying ordinaryrounding techniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the disclosure are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contain certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements. Furthermore, when numerical ranges ofvarying scope are set forth herein, it is contemplated that anycombination of these values inclusive of the recited values may be used.

For molecular weights, whether M_(n) or M_(w), these quantities aredetermined by gel permeation chromatography using polystyrene asstandards as is well known to those skilled in the art and such as isdiscussed in U.S. Pat. No. 4,739,019 at column 4, lines 2-45, which isincorporated herein by reference in its entirety.

As used herein, the terms “polydispersity” and “dispersity” refer to theratio of M_(w) to M_(n), an indicator of the degree of molecular weightdistribution of a polymer and the extent to which the polymer chainsshare the same degree of polymerization. Polydispersity has atheoretical minimum of 1.0. A polymer having a polydispersity of lessthan 1.5, such as 1.35 or less, may be referred to as a monodispersedpolymer.

As used herein, the terms “formed from” and “formed of” denote open,e.g., “comprising,” claim language. As such, it is intended that acomposition “formed from” or “formed of” a list of recited components bea composition comprising at least these recited components, and canfurther comprise other non-recited components during formulation of thecomposition.

As used herein, the term “cure” as used in connection with acomposition, e.g., “a curable material,” “a cured composition,” shallmean that any crosslinkable components of the composition are at leastpartially crosslinked. In certain examples of the present disclosure,the degree of crosslinking can range from 5% to 100% of completecrosslinking. In other examples, the degree of crosslinking can rangefrom 35% to 85% of full crosslinking. In other examples, the degree ofcrosslinking can range from 50% to 85% of full crosslinking. One skilledin the art will understand that the presence and degree of crosslinkingcan be determined by a variety of methods, such as dynamic mechanicalthermal analysis (DMTA) in accordance with ASTM E 1640-99.

As used herein, the term “saturated” or “substantially saturated” meansthat the compound or material of interest is fully saturated (i.e.,contains no double bonds, triple bonds, or aromatic ring structures), orthat the extent of unsaturation is negligible, e.g. as shown by abromine number in accordance with ASTM E234-98 of less than 10, or lessthan 5.

As used herein, the term “flexural modulus” or “modulus” refers to theratio of stress to strain within the elastic limit (measured in flexuralmode) of a material, indicates the bending stiffness of the material,and is similar to tensile modulus. Flexural modulus, typically reportedin Pa or psi, is derived in accordance to ASTM D6272-02.

As used herein, the term “material hardness” refers to indentationhardness of non-metallic materials in the form of a flat slab or buttonas measured with a durometer. The durometer has a spring-loaded indentorthat applies an indentation load to the slab, thus sensing its hardness.The material hardness can indirectly reflect upon other materialproperties, such as tensile modulus, resilience, plasticity, compressionresistance, and elasticity. Standard tests for material hardness includeASTM D2240-02b. Unless otherwise specified, material hardness reportedherein is in Shore D. Material hardness is distinct from the hardness ofa golf ball portion as measured directly on the golf ball (or otherspherical surface). The difference in value is primarily due to theconstruction, size, thickness, and material composition of the golf ballcomponents (i.e., center, core and/or layers) that underlie the portionof interest. One of ordinary skill in the art would understand that thematerial hardness and the hardness as measured on the ball are notcorrelated or convertible.

As used therein, the term “compression,” also known as “Atticompression” or “PGA compression,” refers to points derived from aCompression Tester (ATTI Engineering Company, Union City, N.J.), a scalewell known in the art for determining relative compression of aspherical object. Atti compression is approximately related to Riehlecompression: Atti compression ≈(160-Riehle compression). Compression isa property of a material as measured on a golf ball construction (i.e.,on-ball property), not a property of the material per se.

As used herein, the term “coefficient of restitution” or “CoR” for golfballs or subassemblies thereof is defined as the ratio of a ball'srebound velocity to its initial incoming velocity when the ball is firedout of an air cannon into a stationary, steel plate which provides animpact surface weighing about 100 pounds or about 45 kilograms. The timeperiods, T_(in) and T_(out), of the ball flight between two separateballistic light screens placed between the air cannon and the plate aremeasured to calculate CoR=T_(out)/T_(in). The faster a golf ballrebounds, the higher the CoR it has, the more the total energy itretains when struck with a club, and the longer the ball flies. Thereported CoR's initial velocity is about 50 ft/s to about 200 ft/s, andis usually understood to be 125 ft/s, unless otherwise specified. A golfball may have different CoR values at different initial velocities.

A “Mooney” viscosity is a unit used to measure the plasticity of raw orunvulcanized rubber. The plasticity in a Mooney unit is equal to thetorque, measured on an arbitrary scale, on a disk in a vessel thatcontains rubber at a temperature of 100° C and rotates at tworevolutions per minute. The measurement of Mooney viscosity is definedaccording to ASTM D-1646.

As used herein and to conventional practice, the unit “phr” refers to“parts by weight of a respective material per 100 parts by weight of thebase polymer or polymer blend.”

DETAILED DESCRIPTION

The golf ball of the present invention may comprise any of a variety ofconstructions, but preferably includes a core and a layer (e.g., cover)surrounding the core. The core and/or the cover may have more than onelayer, and one or more intermediate layers may be disposed between thecore and the cover of the golf ball. For example, the core of the golfball may comprise a conventional center surrounded by an intermediate orouter core layer disposed between the center and an inner cover layer,which is encased by an outer cover layer. The innermost portion of thecore may be a liquid filled sphere, but preferably it is solid. As withthe core, the intermediate layer or outer core layer may also comprise aplurality of layers. The core may also comprise a solid or liquid filledcenter around which one or more wound layers are disposed, each woundlayer being formed from one or more tensioned elastomeric materials.

The materials suitable for solid cores or any golf ball layers may bethermoplastic, but preferably partially or fully crosslinked (e.g.,thermoset), and include compositions comprising a base polymer (e.g.,rubber, elastomer) or a blend of two or more base polymers, a crosslinkinitiator or a blend of two or more initiators, and, optionally, one ormore additives (e.g., crosslink coagent, filler, organosulfur compound).

The base polymer or at least one polymer in the base polymer blend canbe crosslinkable (e.g, comprising olefinic and/or acetylenicunsaturation), and include, without limitation, natural and syntheticrubbers (including various raw and reclaim forms), polyolefins,polyamides, polyesters, fluoropolymers, silicones, ionomers, andmixtures thereof. Rubbers and polyolefins include, without limitation,homopolymers and coplymers (including terpolymers and other complexcopolymers, and can be random, block, or grafted types) of ethylene,propylene, butylenes, isobutylene, styrene, and/or dienes (simpledienes, allenes, conjugated dienes, e.g., 1,3-butadiene,2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, chloroprene,1,3-pentadiene, 1,5-hexadiene, 1,3-cyclohexadiene, 1,4-pentadiene,1,4-cyclohexadiene, piperylene), optionally further comprising less than50% of one or more other unsaturated monomers like acetylenes (e.g.,vinyl acetylene), olefins (e.g., isobutylene), vinyls (e.g., acrylicacid, methacrylic acid, ethacrylic acid, propylacrylic acid, otheralkylacrylic acids, C₁₋₆ alkyl esters of such acids, acrylonitrile,styrene, methylstyrene, vinyltoluene, divinylbenzene), vinyl esters,unsaturated aldehydes (e.g., acrolein), unsaturated ketones (e.g.,methyl isopropenyl ketone), unsaturated ethers (e.g., vinyl ether), andothers known to one skilled in the art. Non-limiting examples includepolydienes such as neoprene, polybutadienes (BR, includingcis-1,4-polybutadiene), polyisoprenes (including cis-1,4-polyisoprene),polyethylenes (PE), ethylene-propylene copolymers (EP),ethylene-butylene copolymers, polystyrenebutadienes,polyethylenebutadienes, styrene-propylene-diene terpolymers,ethylene-propylene-diene terpolymers (EPDM, e.g.,ethylene-propylene-dicyclopentadiene termpolymers), butyl rubbers(polyisopreneisobutylene), styprene-isoprene-butadiene terpolymers,copolymers of conjugated diene with styrene, acrylonitrile, and/ormethyl methacrylate, fluorinated polymers thereof (e.g., fluorinated EPand fluorinated EPDM), and blends of one or more thereof. Thecrosslinkable base polymer can be solid at ambient temperature. Suitablecrosslinkable base polymers may have a highly linear structure (e.g.,high cis BR produced by Nd catalyst systems), a highly branchedstructure (e.g., high cis BR produced by Co catalyst systems), or astructure with an intermediate degree of branching (e.g., high cis BRproduced by Ni catalyst systems). Suitable polydiene homopolymers orcopolymers like BR may have high 1,4-cis content (e.g., 60% or greater,80% or greater, 90% or greater, 95% or greater, or about 99% or greater,like high cis BR produced by Nd, Co, or Ni catalyst systems), high1,4-trans content (e.g., 45% or greater, or 55% or greater, or 65% orgreater, or 75% or greater, or 80% or greater, or 90% or greater, likehigh trans BR produced by La, Nd, or Ni catalyst systems), and/or low1,2-vinyl content (e.g., 15% or less, or 10% or less, or 7% or less, or5% or less, or 1% or less). Polydienes like BR can have variouscombinations of cis-, trans-, and vinyl isomer structures, such ashaving a cis-structure content greater than trans-structure contentand/or 1,2-vinyl structure content, with the sum of cis-, trans-, andvinyl isomer contents in any one given polydiene being 100%. Differentpolydienes may be utilized alone or in blends of two or more thereof toformulate different compositions in forming golf ball components(portions or layers within or in between the core and the cover) of anydesirable physical and chemical properties and performancecharacteristics.

Blends of polymers used as the base polymer include, without limitation,those disclosed in co-owned U.S. Pat. No. 6,774,187, the entiredisclosure of which is incorporated herein by reference, as well asblends of two or more polymers chosen from cis-1,4-polyisoprene rubbers,3,4-polyisoprene rubbers, styrene-isoprene-butadiene rubbers, emulsionpolymerization prepared styrene-butadiene rubbers, solutionpolymerization prepared styrene-butadiene rubbers, cis-1,4-polybutadienerubbers, and emulsion polymerization prepared butadiene-acrylonitrile orstyrene-butadiene-acrylonitrile rubbers. The emulsion polymerizationprepared styrene-butadiene rubber, which may enhance processability ofthe uncured composition mixture, may have a styrene content of 5% to18%, or 20% to 28%, or 30% to 50%. The emulsion polymerization preparedbutadiene-acrylonitrile or styrene-butadiene-acrylonitrile rubbers mayhave an acrylonitrile content of 2% to 40% and 2% to 30%, respectively.The solution polymerization prepared styrene-butadiene rubber, which maylower hysteresis of the composition, may have a styrene content of 5% to50%, or 9% to 36%. The cis 1,4-polybutadiene rubber, which may enhanceresiliency and wear of the composition, may have a cis-1,4 content of atleast 90%.

Other parameters used in determining suitable base polymers includeMooney viscosity, solution viscosity, weight and/or number averagemolecular weights, and polydispersity, among others. In one example, thebase polymer or polymer blend may comprise one or more polymers having aMooney viscosity of 35 or greater, or 50 or greater, or a mid-rangeMooney viscosity of 40 to 60, or a high Mooney viscosity of 65 orgreater. The base polymer or polymer blend may have one or more polymershaving a weight average molecular weight of 200,000 or greater, or250,000 or greater, or 300,000 or greater, or 400,000 or greater. Thebase polymer or polymer blend may have one or more polymers having apolydispersity of 2 or less, or 1.8 or less, or 1.5 or less, or 1.35 orless, or 1.2 or less.

In an alternative example, when one or more of the additives disclosedherein is/are used in the composition, the base polymer or polymer blendmay comprise one, two, or more polymers having a Mooney viscosity ofless than 60, or 50 or less, or 35 or less, or 30 or less, or 25 orless, or 20 or less, or 15 or less. The polymer(s) may have a weightaverage molecular weight of 250,000 or less, or 200,000 or less, or180,000 or less, or 150,000 or less, or 100,000 or less, or 85,000 orless, or 50,000 or less. The polymer(s) may have a polydispersity ofgreater than 3.5, or 4 or greater, or 4.5 or greater, or 5 or greater,preferably 10 or less, or 8 or less. The polymer(s) may have a vinylcontent of 8% or greater, or 10% or greater, or 12% or greater, or 15%or greater, or 18% or greater, or 20% or greater, preferably less than40%, or 35% or less, or 30% or less. For instance, the base polymer orpolymer blend may comprise one or more polydienes synthesized using analkyllithium or anionic catalyst system (with or without polar modifierssuch as nitrogen- or oxygen-containing compounds), optionally modifiedby coupling agents and/or reactive compounds with functional groups.

The base polymer blend may further comprise one or more other elastomersthat are crosslinkable or non-crosslinkable, such as diene rubbers andsaturated rubbers known in the art. Suitable elastomers for use in thebase polymer blend include, without limitation, those disclosed hereinabove, partially and/or fully hydrogenated versions thereof, as well aspolyurethane rubbers, polyurea rubbers, metallocene-catalyzed polymers,plastomers, and multi-olefin polymers, which may be homopolymers,copolymers, or terpolymers. With a major portion (e.g., 50% or greaterby weight of the base polymer blend, or 80% or greater) of the basepolymer blend being one or a combination of two or more crosslinkablepolymers, such as polydienes, preferably polybutadienes, these othermiscible elastomers can be present in amounts of less than 50%, or 40%or less, or 30% or less, or 25% or less, or 20% or less, or 15% or less,or 10% or less, or 5% or less. In one example, the base polymer blendcomprises less than 20% balata, or 18% or less, or 10% or less. Inanother example, the base polymer is substantially free of balata (i.e.,2% or less).

A preferred base rubber is 1,4-polybutadiene having a cis-structure ofat least 40%, more preferably at least about 90%, and most preferably atleast about 95%. Most preferably, the base rubber compriseshigh-Mooney-viscosity rubber. Preferably, the base rubber has a Mooneyviscosity greater than about 35, more preferably greater than about 40,most preferably greater than about 50. Preferably, the polybutadienerubber has a molecular weight greater than about 200,000, morepreferably 275,000 or greater, most preferably 400,000 or greater, and apolydispersity of no greater than about 3, more preferably 2 or less.Examples of desirable polybutadiene rubbers include BUNA® CB22 and BUNA®CB23, commercially available from Bayer of Akron, Ohio, UBEPOL® 360L andUBEPOL® 150L, commercially available from UBE Industries of Tokyo,Japan, and CARIFLEX® BCP820 and CARIFLEX® BCP824, commercially availablefrom Shell of Houston, Tex. If desired, the polybutadiene can also bemixed with other elastomers known in the art such as natural rubber,polyisoprene rubber and/or styrene-butadiene rubber in order to modifythe properties of the core.

Crosslink initiators include any chemical and/or physical means known oravailable to one skilled in the art, particularly those that are capableof generating reactive free radicals, like thermal initiators andphotoinitiators. Such initiators include, but are not limited to,compounds such as elemental sulfur or sulfur donors (with or withoutaccelerators), organic peroxides, organometallic peroxides,carbon-carbon initiators, azo compounds (e.g., azobisisobutylonitrile),peresters, organic polyoxides, ozone, dioxygen, Haloid molecules,polyatomic peroxides, substituted hydrazines, hydrazides, benzophenones,alkoxyamines, nitro compounds, nitrates, nitrites, disulfides,polysulfides and organometallic compounds, as well as radiation means(with or without one or more sensitizers, like photoinitiators) such asactinic radiation, particle radiation, X-ray irradiation, electron beamirradiation, ultrasound, and heating, or a combination of two or more ofsuch compounds and/or physical means. Initiator decomposition promotersmay be used in combination with the various initiators and blendthereof. When one or more initiator compounds are used in the pure form,the amount of the total initiators may be 0.1 phr or greater, or 0.2 orgreater, or 0.5 phr or greater, or 0.8 phr or greater, preferably 10 phror less, or 5 phr or less, or 2 phr or less, or 1 phr or less. Theweight ratio between any two initiator compounds, when used together,can be 0.05:1 to 50:1, or 0.1:1 to 5:1, or 0.25:1 to 3:1, or 0.5:1 to1:1, or any other ranges there between. When the initiator decompositionpromoters are used, the molar ratio of the promoter to the initiator maybe 0.001:1 to 1:1, or 0.05:1 to 0.1:1.

The initiator can be any known polymerization initiator which decomposesduring the cure cycle. Suitable initiators include organic peroxidecompounds, such as peroxy ketals (e.g.,1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane,1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane,n-butyl-4,4-bis(t-butylperoxy)valerate,2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane,1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane,1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane,2,2-bis(t-butylperoxy)octane), dialkyl peroxide (e.g., dicumylperoxide(DCP), α,α-bis(t-butylperoxy)diisopropylbenzene (DTBP),2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butylperoxide,di-t-amylperoxide, t-butylcumylperoxide,di(2-methyl-1-phenyl-2-propyl)peroxide,t-butyl-2-methyl-1-phenyl-2-propylperoxide,2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,di(2-t-butyl-peroxyisopropyl)benzeneperoxide), diacyl peroxides (e.g.,isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide,3,5,5-trimethylhexanoyl peroxide, m-toluoylbenzoyl peroxide,benzoylperoxide, m-toluoylperoxide,2,5-dimethyl-2,5-di(benzoylperoxy)hexane, acetyl peroxide,propionylperoxide, octanoylperoxide, decanoylperoxide, lauroylperoxide,stearoylperoxide, succinic acid peroxide, t-butyl-peroxymaleic acid),peroxy esters (e.g., .alpha.,.alpha.-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxy neodecanoate,1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexyl peroxyneodecanoate, t-butylperoxyneodecanoate, t-hexyl peroxypivarate, t-butyl peroxypivarate,1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate,2,5-dimethyl-2,5-bis(2-ethylhexanoyl peroxy)hexane,1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butyl peroxymaleic acid,2,5-dimethyl-2,5-bis(m-toluoyl peroxy)hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexyl peroxy benzoate,2,5-dimethyl-2,5-bis(benzoyl peroxy)hexane, t-butyl peroxy-m-toluoylbenzoate, bis(t-butyl peroxy)isophthalate,t-butyl-peroxyisopropylcarbonate, t-butylperoxyacetate,t-butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate,t-butylperoxylaurate, t-butylperoxybenzoate), ketone peroxides (e.g.,methylcyclohexanone peroxide, methylacetoacetate peroxide, acetylacetoneperoxide, methylethylketone peroxide, cyclohexanone peroxide),hydroperoxides (e.g., t-hexyl hydroperoxide, t-butylhydroperoxide,p-menthanehydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide,2,5-dimethylhexane-2,5-dihydroperoxide, cumenehydroperoxide,diisopropylbenzenehydroperoxide), peroxydicarbonates (e.g., di-n-propylperoxydicarbonate, diisopropyl peroxydicarbonate,bis(4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-methoxybutylperoxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate),t-butyltrimethylsilyl proxide, 3,3′, 4,4′-tetra(t-butylperoxycarbonyl)benzophenone, and mixtures of two or more thereof. DCP isthe most commonly used peroxide in golf ball manufacturing. DTBP canprovide higher crosslinking efficiency, low odor and longer scorch time,among some properties. DCP can be blended with DTBP for use in golfballs. Other examples include, but are not limited to, VAROX® 231XL andVarox® DCP-R, commercially available from Elf Atochem of Philadelphia,Pa., PERKODOX® BC and PERKODOX® 14, commercially available from AkzoNobel of Chicago, Ill., and ELASTOCHEM® DCP-70, commercially availablefrom Rhein Chemie of Trenton, N.J.

It is well known that peroxides are available in a variety of formshaving different activity. The activity is typically defined by the“active oxygen content.” For example, PERKODOX® BC peroxide is 98%active and has an active oxygen content of 5.80%, whereas PERKODOX®DCP-70 is 70% active and has an active oxygen content of 4.18%. If theperoxide is present in pure form, it is preferably present in an amountof at least about 0.25 phr, more preferably between about 0.35 phr andabout 2.5 phr, and most preferably between about 0.5 phr and about 2phr. Peroxides are also available in concentrate form, which arewell-known to have differing activities, as described above. In thiscase, if concentrate peroxides are employed in the present invention,one skilled in the art would know that the concentrations suitable forpure peroxides are easily adjusted for concentrate peroxides by dividingby the activity. For example, 2 phr of a pure peroxide is equivalent to4 phr of a concentrate peroxide that is 50% active (i.e., 2 divided by0.5=4).

Carbon-carbon initiators include those described in co-pending andco-owned U.S. Application Publication No. 2005-0009992, the disclosureof which is incorporated herein by reference in its entirety.Carbon-carbon initiators may be used in place of the peroxideinitiators, or in blends with the peroxide initiators, the weight ratiobetween which is described above.

Initiator decomposition promoters may be used in combination with one ormore of the additives described herein (e.g., boron-containingcompounds). Useful promoters include, without limitation, iron (III)compounds (e.g., iron chloride, iron acetylacetonate, iron naphthenate,iron citrate), copper (II) compounds (e.g., copper chloride, coppercitrate, copper acetylacetonate, copper stearate), molybdenum compounds(e.g., molybdenum (VI) oxide, molybdenum oxide acetylacetonate, andthose disclosed herein), manganese compounds (e.g., manganese (IV)oxide, manganese naphthenate, and those disclosed herein), cobaltcompounds (e.g., cobalt naphthenate, cobalt (III) acetylacetonate),tungsten compounds (e.g., tungsten (VI) oxide, sodium tungstate,silicotungstic acid, and those disclosed herein), tin compounds (e.g.,dibutyltin (IV) oxide, and those disclosed herein), and metal alkoxides(e.g., titanium tetrabutoxide, aluminum tributoxide, and those disclosedherein).

Functional additives may serve a single function, or two, three, or morefunctions, including, without limitation, peptizer, plasticizer (e.g.,physical, crosslinking), isomerization agent, crosslink co-agent, freeradical mediator (e.g., sulfur donor), photoinitiator, oxidizer,sensitizer, synergizer, flame-retardant, impact modifier, thermalstabilizer, antistatic agent, compatibilizing agent, foaming agent,reinforcing agent, initiator decomposition promoter, viscosity impartingagent, polymerization adjusting agent, surface treating agent, coloringagent, perfume, processing aid, coupling agent, accelerator, activator,antidegradant, antioxidant, dilatant agent, dispersant, enhancer (e.g.,for CoR), reducer (e.g., for compression, crystallinity), extender,filler (e.g., for density, modulus), inhibitor, lubricant, retarder(e.g., cure, scorch), scavenger (e.g., for oxygen, moisture, freeradical), stabilizer (e.g., thermal, light, degradation), thixotropicagent, and/or wetting agent. Preferably, the additives may be a CoRenhancer (i.e., capable of increasing CoR of the core and/or the ball),isomerization mediator (e.g., capable of changing the percentages ofcis, trans, and/or vinyl contents in the base polymer), crystallinityreducer (i.e., capable of decreasing the degree of crystallinity in theformed golf ball core or layer), T_(g) shifter (i.e., capable ofshifting glass transition temperature (T_(g)) curve (determined by adifferential scanning calorimeter or a dynamic mechanical analyzer) ofthe polymer material up or down the temperature scale), modulator fordegree of crosslink (i.e., capable of changing the degree of one or moretypes of crosslink: polymer-polymer crosslink, coagent-polymercrosslink, coagent-coagent crosslink, carbon-carbon crosslink, ioniccrosslink), and/or crosslink profile modulator (i.e., capable ofchanging the ratio of different crosslink types). The additive may exertone or more of such functions (e.g., being a CoR enhancer) without oneor more of the other functions (e.g., without being a isomerizationmediator). Additives may provide different functions at the same time,or at different stages during material process, ball manufacturing,storage, and/or usage.

One group of suitable additives have the structure

where at least one (e.g., 2, 3, 4, or 5) of R₁, R₂, R₃, R₄, and R₅ arethe same or different electron-withdrawing groups (“EWG”); the remainderof R₁ to R₅, if any, are the same or different organic radicals, orhydrogen; Z is chosen from metal cations (monovalent, divalent, or otherpolyvalent, e.g., Li, Na, K, Cs, Be, Mg, Ca, Sr, Ba, Ti, Zr, Cr, Mo, Fe,Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, Cd), organometallic cations (such asthose disclosed herein), and non-metal organic cations (e.g., ammonium,substituted ammonium, trityl, and any of those disclosed herein), or mayalso be H or halogen when n is 1 (e.g., arylsulfenyl halides); and n isan integer of 1, 2, or greater, preferably 6 or less.

In one example, the EWG is preferred EWG (“PEWG”) chosen from C₁₋₁₂perhaloalkyls (including linear and branched ones, having 1, 2, 3, 4, 5,6, or more carbon atoms and 1, 2, 3, or more types of halogens, e.g.,linear C₂₋₈ perhaloalkyls, branched C₃₋₆ perhaloalkyls), C₆₋₂₀(per)haloaryls (including those having aromatic rings of 6 or morecarbon atoms and 1, 2, 3, or more types of halogen substituents), C₇₋₂₀(per)haloaralkyls (including those having 1, 2, 3, or more types ofhalogen substituents), C₇₋₂₀ (per)haloalkaryls (including those having1, 2, 3, or more types of halogen substituents), C₃₋₂₀(per)halocycloalkyls (including those having cyclic structures of 3 ormore carbon atoms and 1, 2, 3, or more types of halogen substituents),and combinations of two or more thereof. EWG other than perhaloalkylscan be free of halogen substitution, partially halogenated, orperhalogenated. Halogens include F, Cl, Br, and I. Non-limiting examplesof such EWG include —CF₃, —CCl₃, —CBr₃, —CI₃, C₂₋₈ (per)fluoroalkyls,C₂₋₈ (per)chloroalkyls, C₂₋₈ (per)bromoalkyls, C₂₋₈ (per)iodoalkyls,—C(CF₃)₃, —C(CCl₃)₃, —C(CBr₃)₃, —C(CI₃)₃, (per)fluorocycloalkyls,(per)chlorocycloalkyls, (per)bromocycloalkyls, (per)iodoocycloalkyls,(per)halophenyls (e.g., p-bromophenyl, m-bromophenyl, p-chlorophenyl),—C(X₁)₂X₂, —CX₁X₂H, and —CX₁X₂X₃, where X₁, X₂, and X₃ are differenthalogens. Preferably, one or more (e.g., two or three) of R₁, R₃ and R₅is/are the same or different species of EWG described above. It isbelieved that these preferred EWG are more electron-withdrawing thanother EWG described herein below, thus are more effective in carryingout their desired functions.

Other non-limiting EWG for R₁ to R₅ include X (halogens), aldehyde,[(per)halo]alkyl/aryl carbonyl (COR, e.g., acetyl, trifluoroacetyl,phenylcarbonyl), COOZ (carboxylic acid or salt thereof), COOR([(per)halo]ester, [(per)halo]alkyl/aryl oxycarbonyl, e.g.,methoxycarbonyl, ethoxycarbonyl), COX (halocarbonyl), SR such as(per)halo(cyclo)alkylthio having 1, 2, 3 or more carbon atoms (e.g.,trifluoromethylthio) and (per)haloarylthio having 6 or more carbonatoms, SO₂NH₂ (sulfonamide), SO₂NHR ([(per)halo]sulfonamide), SO₂NR₂([(per)halo]sulfamoyl), SCOR ([(per)halo]carbonylthio, e.g.,acetylthio), [(per)halo]amido (e.g., amido, methylamido, phenylamido,ureido), SCONH₂ (carbamoylthio), SOR ([(per)halo]alkyl/aryl oxythio,e.g., methoxylthio), SO₂R ([(per)halo]alkyl/aryl sulfonyl, e.g.,methylsulfonyl, phenylsulfonyl), CN (nitrile or cyano), SO₃Z (sulfonicacid or salt thereof), SO₃R ([(per)halo]sulfonate ester), N^(⊕)H₃,N^(⊕)R₃, NO₂ (nitro), and NCS (thiocyanato), where R is the same ordifferent, optionally substituted (e.g., (per)halogenated), C₁₋₂₀monovalent radicals, such as C₁₋₁₈ alkyls (including linear or branchedones), C₃₋₈ cycloalkyls, C₆₋₁₅ aryls, and C₇₋₂₀ aralkyls.

Suitable radicals for the remainder of R₁ to R₅ further include H,linear, branched, or cyclic monovalent radicals having one or morecarbon atoms, alkyls (e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl,s-butyl, n-pentyl, n-hexyl), aryls (e.g., phenyl, α-naphthyl,β-naphthyl), alkaryls (e.g., p-methylphenyl), aralkyls (e.g., benzyl,phenethyl), alkenyls (e.g. vinyl), aralkenyls (e.g., 2-phenylvinyl),alkynyls (e.g., ethynyl, propargyl, 2-butynyl), aralkynyls (e.g.,phenethynyl), EWG-substituted aryls, [(per)halo]alkenyls (e.g., —CH═CR₂,—CX═CR₂), [(per)halo]alkynyls (C≡CR), SH (thio), OH (hydroxyl), OR suchas [(per)halo]alkoxy (e.g., trifluoromethoxy, methoxy, ethoxy, propoxy,butoxy, pentyloxy, hexyloxy, isopropoxy, isobutoxy, isopentyloxy), C₃₋₈[(per)halo]cycloalkyloxy (e.g., cyclopropyloxy, cyclohexyloxy,cyclohexylmethoxy), C₆₋₁₅ [(per)halo]aryloxy (e.g., phenyloxy,p-tolyloxy), C₇₋₂₀ [(per)halo]aralkyloxy (e.g., benzyloxy, phenethyloxy,diphenylmethoxy, triphenylmethoxy), C₇₋₁₀ [(per)halo]phenylalkyloxy,C₇₋₁₀ [(per)halo]alkylphenyloxy, C₂₋₇ [(per)halo]acyloxy (e.g.,acetyloxy, propionyloxy, acryloyloxy, benzoyloxy), C₂₋₆[(per)halo]alkenyloxy (e.g., vinyloxy, 1-propenyloxy, allyloxy), C₂₋₆[(per)halo]alkynyloxy (e.g., ethynyloxy, 2-propinyloxy), C₂₋₇[(per)halo]alkoxycarbonyloxy (e.g., methoxycarbonyloxy,ethoxycarbonyloxy), C₇₋₁₅ [(per)halo]aryloxycarbonyloxy (e.g.,phenoxycarbonyloxy, benzyloxycarbonyloxy), C₁₋₇[(per)halo]alkanesulfonyloxy (e.g., methanesulfonyloxy,ethanesulfonyloxy), and C₆₋₁₀ [(per)halo]arylsulfonyloxy (e.g.,benzenesulfonyloxy), and hydroxyalkyls (e.g., hydroxymethyl). Any of theorganic radicals described herein may be partially or fully halogenatedwith one or more types of halogens.

Non-limiting examples of the group of additives having the preferredEWG, as described above, include 2-, 3-, or4-(trifluoromethyl)thiophenol, 2-, 3-, or 4-(trichloromethyl)thiophenol,2-3-, or 4-(tribromomethyl)thiophenol, 2-, 3-, or4-(triiodomethyl)thiophenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or3,5-bis(trifluoromethyl)thiophenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or3,5-bis(trichloromethyl)thiophenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or3,5-bis(tribromomethyl)thiophenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or3,5-bis(triiodomethyl)thiophenol, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-or 3,4,5-tris(trifluoromethyl)thiophenol, 2,3,4-, 2,3,5-, 2,3,6-,2,4,5-, 2,4,6- or 3,4,5-tris(trichloromethyl)thiophenol, 2,3,4-, 2,3,5-,2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-tris(tribromomethyl)thiophenol, 2,3,4-,2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-tris(triiodomethyl)thiophenol,and metal salts (e.g., Zn, Co, Mg) thereof.

Another group of additives have the general structure

where at least one of R₁, R₂, R₃, R₄ and R₅, and at least one of R₆, R₇,R₈, R₉, and R₁₀ are the same or different radicals chosen from PEWG,—SZ, and —OZ, where PEWG and Z are described above; the remainder of R₁to R₁₀, if any, are the same or different radicals chosen from H andother EWG and organic substituents, such as those described above; and nis an integer of 1, 2, 3, 4, or greater. In one example, at least one(e.g., two or three) of R₁, R₃ and R₅ and/or at least one (e.g., two orthree) of R₆, R₈ and R10 is/are the same or different PEWG. In anotherexample, at least one (e.g., two or three) of R₁, R₃ and R₅ and/or atleast one (e.g., two or three) of R₆, R₈ and R₁₀ is/are the same ordifferent —SZ or —OZ. Non-limiting examples of such additives include4,4′-thiobisbenzenethiol, bithionol, dichlorodiphenylsulfide,bis(4-methoxyphenyl)disulfide, bis(3-methoxyphenyl)disulfide,bis(2-methoxyphenyl)disulfide, bis(4-ethoxyphenyl)disulfide,bis(4-isopropoxyphenyl)disulfide, bis(4-cyclohexyloxyphenyl)disulfide,bis(4-allyloxyphenyl)disulfide, bis[4-(2-propinyloxy)phenyl)disulfide,bis(4-phenoxyphenyl)disulfide, bis(4-acetoxyphenyl)disulfide,bis(4-benzoyloxyphenyl)disulfide,bis(4-methanesulfonyloxyphenyl)disulfide,bis(4-benzenesulfonyloxyphenyl)disulfide,bis(4-methoxycarbonyloxyphenyl)disulfide,bis(4-phenoxycarbonyloxyphenyl)disulfide,bis(4-trifluoromethylphenyl)disulfide,bis(4-trichloromethylphenyl)disulfide,bis(4-tribromomethylphenyl)disulfide, and salts thereof, like zinc4,4′-thiobisbenzenethiol and sodium bithionolate.

Without being bound to any particular theory, it is believed that thepresence of one or more EWG on the aromatic structures, particularly atortho and/or para positions, decreases electron densities along the S—S,S—Z, and/or C—S bonds, thereby decreasing their bond dissociationenergy, making the bonds readily dissociate, particularly under theconditions of conventional cure cycle (e.g., in the presence of heat andcrosslink initiator). Such bond dissociations lead to the formation ofradical intermediates, which in turn may affect the long chains of thebase polymer. In particular, the radical intermediates may affect theformation of one or more types of crosslink during cure, therebyenhancing resiliency of the resulting molded product, with or withoutconcomitant impact on its other properties (e.g., compression, hardness,flexural modulus). It is further believed that the radical intermediates(e.g., thiyl radicals) may be capable of mediating hydrogen atomtransfer reaction, which can result, at least partially, in cis-transisomerization.

Another group of additives have the general structure

where at least one (e.g., two, three, or more) of R₁, R₂, R₄, and R₅ is—OZ or, preferably, —SZ, Z being described above; the remainder ofsubstitutents R₁ to R₅, if any, are the same or different radicalschosen from H, EWG, and organic substituents such as those describedabove; n is 1 when Z is H or halogen, or an integer of 1 to 6 when Z isa cation. In one example, at least one of R₁ and R₅ is —SZ. In anotherexample, R₃ is also —SZ. Alternatively, R₃ is an organic group otherthan —SZ. Non-limiting examples of such additives include ortho-dithiolsand ortho-polythiols, such as 1,2-dithiolbenzene, 3,4-dithioltoluene,3,4,5,6-tetrachloro-1,2-dithiolbenzene, 1,2,4,5-tetrathiolbenzene,1,2-benzenedithiol zinc salt, 3,4-toluenedithiol zinc salt,3,4,5,6-tetrachloro-1,2-benzenedithiol zinc salt,1,2,4,5-benzenetetrathiol dizinc salt, 4,4′-thiobisbenzenethiol dizincsalt, 2,2′-thiobis(4,6-dichlorophenol) disodium salt.

Other suitable additives that are organosulfur compounds include organicsulfides, and their metal salts, as well as metal salts of aromaticortho-thiols. Suitable organosulfur compounds include:1,3-dithiolane,2,4,5-trithione, and its oligomer;1,3,4,6-tetrathiapentalene-2,5-dione; 2-thiobarbituric acid;2-thiouracil; 2,2′-dithiobis(pyridine-N-oxide);2,2′-thiobis(4,6-dichlorophenol) disodium salt;2,2′-(2,5-thiophenediyl)bis[5-tert-butylbenzoxazole];3-mercaptopropionic acid zinc salt; 3-(phenylthio)acrylic acid;3,5-dichlorobenzenesulfonyl chloride; 4-thiouracil;4,4′-bis(diphenylsulfonium)diphenylsulfide hexafluoroantimony salt;4,4′-thiobisbenzenethiol dizinc salt;6-amino-1,3,5-triazine-2,4-dithiol; 8,8′-quinolyl disulfide;acryloxythiol; acryloxythiol zinc salt; ammoniumpyrrolidinecarbodithioate; benzene-1,2-dicarbodithioic acid;benzene-1,2-dicarbothioic acid; benzenedisulfonyl chloride;benzenesulfinic acid sodium salt; benzenesulfonamide; benzenesulfonicacid; benzoyldisulfide; benzo[c]thiophene-1,3-dione;benzo[c]thiophene-1,3-dithione; benzyl N,N-dimethyldithiocarbamate;bis(3-triethoxysilylpropyl)tetrasulfide;bis(4-acryloxybenzene)disulfide; bis(phenylsulfonyl)methane; butadienesulfone; di-p-toluenesulfonamide; di-p-tolyldisulfone;di-p-tolyldisulfoxide; di-p-tolylsulfinyl sulfone;Di-(4-acryloxyphenyl)disulfide; diisopropylxanthogen disulfide; dimethylsulfite; diphenyl-(4-phenylsulfanyl-phenyl)-sulfonium hexafluoroantimonate (V); diphenyl disulfone; diphenyldichlorosulfide;diphenylsulfone; diphenylsulfoxide; formamidine disulfidedihydrochloride; glyoxal sodium bisulfite addition compound, hydrate;manganese ethylenebis(dithiocarbamate); methanesulfonamide;N-chloro-p-toluenesulfonamide, sodium salt; N-(cyclohexylthio)phthalimide; N-(phenylthio)phthalimide; N,N′-sulfonylbisaniline;p-toluenesulfinic acid sodium salt; p-toluenesulfonamide;p-toluenesulfonyl hydrazide; pentafluorobenzenesulfenyl chloride;phenothiazine; phenoxathiin; phenylsulfonylhydride; polysulfide rubber;poly(p-phenylene ether-sulfone); poly(phenylene sulfide); s-trithiane;sulfanilamide; sulfanilic acid; sulfolane; sulfothioquinoline;tetraalkylthiuramdisulfides; tetraamylthiuramdisulfide;tetrachloropyridinethiol; tetrathiafulvalene; thianthrene;thiobis(triphenyl sulfonium hexafluorophosphate); thionin acetate;thionin perchlorate; thionine chloride; thiophthalic acid; thiophthalicanhydride; thiosemicarbazide; thiourea; thioxanthen-9-one;toluene-3,4-dithiol zinc salt; triphenylsulfonium tetrafluoroborate;triphenylsulfur chloride; zinc 2-mercaptopyridine-N-oxide; zinc2-mercaptotoluimidazole; zinc benzenesulfinate dihydrate; zincDi-n-butyldithiocarbamate; zinc dimethyldithiocarbamate; zincdi(acrylthioic acid); zinc isopropyl xanthate; zinc p-toluenesulfonate,and (4-phenylthiophenyl)diphenylsulfonium triflate.

Suitable metal salts of aromatic ortho-thiols include those having thegeneral structure

where n is an integer from 1 to 2, 4 or 6, m is an integer from 1 to 3,and x is an integer from 1 to 6, and where substitutents R₁ to R₄ arethe same or different radicals chosen from H, S and EWG such as thosedescribed above. Specific non-limiting examples include1,2-benzenedithiol zinc salt; 3,4-toluenedithiol zinc salt;3,4,5,6-tetrachloro-1,2-benzenedithiol zinc salt, and1,2,4,5-benzenetetrathiol dizinc salt.Another group of suitable additives include inorganic-sulfur compounds(i.e., sulfur-containing compounds that are free of sulfur-to-carbon(i.e. organosulfur) covalent bonds, but have covalent and/or ionic bondsbetween sulfur and non-carbon atoms like O, N, P, Si, metals, and thelike), preferably carbon-containing inorganic-sulfur compounds, and morepreferably carbon-containing inorganic-sulfides), non-metalinorganic-sulfur compounds (preferably non-metal inorganic-sulfides),inorganic-thiols, metal sulfides, and derivatives thereof. Non-limitingexamples of carbon-containing inorganic-sulfur compounds includeammonium diethyldithiophosphate; dithiophosphate diethyl ester;piperidine tetrathiotungstate, and glycol sulfite. Non-limiting examplesof carbon-containing inorganic-sulfides include zincdi-n-butyldithiophosphate; bis(triphenyltin)sulfide;bis(diphenylphosphine) disulfide; diphenyltin sulfide; triphenylantimonysulfide; triphenylphosphine sulfide;2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide(Lawesson's Reagent), and dithiobispentamethylcyclotrisiloxane.Non-limiting examples of suitable non-metal inorganic-sulfides includenitrogen sulfide; phosphorous pentasulfide; phosphorous trisulfide;iodosulfide; iododisulfide; polythiazyl, or tetrathionic acid.Non-limiting examples of inorganic-thiols include dithiophosphatediethyl ester; tetrathiotungstic acid; thiostannic acid; sodiumhydrosulfide. Non-limiting examples of metal sulfides include sodiumpolysulfide; barium sulfide; antimony (V) sulfide, and ammoniumtetrathiomolybdate. Non-limiting examples of non-metal inorganic-sulfurcompounds include sulfamide; sulfonyldihydrazine; sulfur iodide, andammonium thiosulfate.

Another group of suitable additives are halogenated hydrocarbons, suchas halogenated alkanes, or halogenated alkenes, or halogenated alkynes,or aromatic-containing halogenated alkanes, includingaromatic-containing halogenated alkanes with EWG on the aromatic ring. Anon-limiting example of a suitable halogenated alkane is1-bromooctadecane. Non-limiting examples of aromatic-containinghalogenated alkanes include ortho, meta, or para-xylylene dibromide, orchlorotriphenylmethane.

Another group of suitable additives are inorganic-halides (i.e.,halogen-containing compounds having at least one covalent and/or ionicbond between a halogen atom and a non-carbon atom like O, N, P, Si, andmetals, but may or may not have halogen-to-carbon covalent bonds), andinclude carbon-containing inorganic-halides. Non-limiting examples ofinorganic-halides include zinc chloride; zinc iodide; ammonium iodide;iodosulfide; iododisulfide; ruthenium (III) chloride hydrate; seleniumdichloride; selenium oxychloride; sulfur iodide; tellurium dichloride;titanium (IV) chloride; vanadium (III) chloride; diphosphorustetraiodide, and hexachlorocyclotriphosphazene. Non-limiting examples ofcarbon-containing inorganic-halides include bicyclo[2.2.1]hepta-2,5-diene-rhodium(I) chloride dimmer;bis(cyclopentadienyl)zirconium chloride; bis(cyclopentadienyl)zirconiumchloride hydride; cyclopentadienyl titanium(IV) trichloride; diphenyliodonium iodide; diphenyl selenium dichloride; diphenyldichlorosulfide;diphenyltin dichloride; N-bromosuccinimide;p-xylylenebis(triphenylphosphoniumbromide); pentafluorobenzenesulfenylchloride; phenylselenyl bromide; polymer-bound selenium bromide;tellurium dichloride complex with thiourea (1:2); tetraethylammoniumbromide; triphenylselenium chloride; triphenylsulfur chloride;1,2-phenylene phosphorochloridite; 3,5-dichlorobenzenesulfonyl chloride;dicyclopentadienyltitanium dichloride; trimethylphenylammonium iodide;tosyl chloride; trichloroisocyanuric acid; benzenedisulfonyl chloride;trichloromelamine; chlorotrimethylsilane, and diphenyl phosphinechloride.

Another group of suitable additives are aromatic ethers (i.e., compoundshaving at least one ether linkage with at least one end linked to anaromatic structure, preferably the aromatic structure is substitutedwith one or more EWG as described herein above, more preferably the EWGis halogen and/or halogenated structures like PEWG), and includecompounds having the general structure

where R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ are or differentradicals chosen from H, EWG, —SZ, and —OZ, such as those describedabove. In one example, at least one (e.g., two or three) of R₁, R₃ andR₅ and/or at least one (e.g., two or three) of R₆, R₈ and R₁₀ is/are thesame or different EWG as disclosed herein above. In another example, theadditive is a halogenated aromatic ether. A non-limiting example ofaromatic ethers is 1,3-diphenoxybenzene. Non-limiting examples ofhalogenated aromatic ethers include 4-bromophenyl ether;pentabromophenyl ether; pentachlorophenyl ether, or pentafluorophenylether.

Another group of suitable additives are acids and derivatives thereof.These include stannic acids, aliphatic sulfonic acids and their salts,halogenated aliphatic sulfonic acids and their salts, aromatic sulfonicacids and their salts, halogenated aromatic sulfonic acid and theirsalts, aromatic sulfinic acids and their salts, halogenated aromaticsulfinic acids and their salts, inorganic sulfates, inorganicpersulfates, inorganic sulfites, inorganic bisulfites, tetrathioic acidsand their salts, inorganic thiosulfates, sulfamic acids and their salts,sulfanilic acids and their salts, aromatic thiophthalates and theirderivatives, thioaromatic acids, thiobarbituric acids,pyrrolidinecarbodithioic acids and their salts, iodic acid and itssalts, inorganic tetrathio acids and their salts, aliphaticdithiophosphoric acids and their salts, aromatic dithiocarbamic acidsand their salts, aromatic carboxylic acids and their salts, halogenatedaromatic carboxylic acids, halogenated carboxylic acids and their salts,and sulfuric acid amides. Non-limiting examples of stannic acidsinclude: metastannic acid; thiostannic acid, and chlorostannic acid.Non-limiting examples of aliphatic sulfonic acids and their saltsinclude methane sulfonic acid, or sodium ethanesulfonate. Non-limitingexamples of halogenated aliphatic sulfonic acids and their salts includetrifluoromethane sulfonic acid; potassium chloromethane sulfonate, andzinc triflate. Non-limiting examples of aromatic sulfonic acids andtheir salts include benzenesulfonic acid; p-toluenesulfonic acid, orzinc tosylate. Non-limiting examples of suitable halogenated aromaticsulfonic acid and their salts include dichlorobenzenesulfonic acid, andammonium fluorobenzenesulfonate. Non-limiting examples of aromaticsulfinic acids and their salts include benzenesulfinic acid; zincbenzenesulfinate, or sodium toluenesulfinate. Non-limiting examples ofhalogenated aromatic sulfinic acids and their salts includepentachlorobenzenesulfinic acid, and zinc trichlorotoluenesulfinate.Non-limiting examples of suitable inorganic sulfates include calciumsulfate, and ammonium sulfate. Non-limiting examples of inorganicpersulfates include potassium persulfate, and ammonium persulfate.Non-limiting examples of inorganic sulfites include sodium sulfite;ammonium sulfite, or potassium metabisulfite. Non-limiting examples ofinorganic bisulfites include sodium bisulfite, and zinc bisulfite.Non-limiting examples of tetrathioic acids and their salts includetetrathionic acid; sodium tetrathionate, and zinc tetrathionate.Non-limiting examples of inorganic thiosulfates include ammoniumthiosulfate; barium thiosulfate, or calcium thiosulfate. Non-limitingexamples of suitable sulfamic acids and their salts include sulfamicacid; ammonium sulfamate, and nickel sulfamate. Non-limiting examples ofsuitable sulfanilic acids and their salts include sulfanilic acid;sodium sulfanilate, and zinc sulfanilate. Non-limiting examples ofaromatic thiophthalates and their derivatives include thiophthalic acid,and thiophthalic anhydride. Non-limiting examples of thio aromatic acidsinclude (3-phenylthio) acrylic acid, and chlorophenylthio acetic acid. Anon-limiting example of a thiobarbituric acid is 2-thiobarbituric acid.Non-limiting examples of pyrrolidinecarbodithioic acids and their saltsinclude 1-pyrrolidinecarbodithioic acid, or ammoniumpyrrolidinecarbodithioate. Non-limiting examples of iodic acid and itssalts include iodic acid; sodium iodate, and zinc iodate. Non-limitingexamples of inorganic tetrathio acids and their salts includetetrathiotungstic acid; ammonium tetrathiotungstate, or piperidinetetrathiotungstate. Non-limiting examples of suitable aliphaticdithiophosphoric acids and their salts include dimethyldithiophosphoricacid, and zinc di-n-butyldithiophosphate. Non-limiting examples ofaromatic dithiophosphoric acids and their salts includediphenyldithiophosphoric acid, or zinc ditolyldithiophosphate.Non-limiting examples of aliphatic dithiocarbamic acids and their saltsinclude dimethyl dithiocarbamate; manganeseethylenebis(dithiocarbamate); manganese zincethylenebis(dithiocarbamate); disodium ethylenebis(dithiocarbamate), andzinc dibutyl dithiocarbamate. A non-limiting example of an aromaticdithiocarbamic acids or its salt is zinc ethyl phenyl dithiocarbamate.Non-limiting examples of aromatic carboxylic acids and their saltsinclude benzoic acid; trimellitic acid; 4-hydrazinobenzoic acid;phthalic acid, or zinc benzoate. Non-limiting examples of halogenatedaromatic carboxylic acids and their salts include chlorobenzoic acid,and zinc pentachlorobenzoate. Non-limiting examples of halogenatedcarboxylic acids and their salts include trichloroacetic acid;trifluoroacetic acid, or sodium chloroacetate. A non-limiting example ofa sulfuric acid amide is sulfamide.

Another group of additives suitable to enhance CoR or reduce compressionare organoselenium compounds, including organic selenides (e.g.,diselenides and higher polyselenides), organoselenyl halides, aromaticselenocompounds (e.g., aromatic selenides, (di)aryl selenocompounds),and their derivatives, preferably aromatic selenides, more preferablywith the aromatic structure substituted with one or more EWG disclosedherein, and most preferably halogenated aromatic selenides. Anon-limiting example of an organoselenium compound is benzeneselenol. Anon-limiting example of an organic selenide compound istetramethyltetraselenafulvalene. Non-limiting examples of aromaticselenides include diphenyl diselenide; phenyl selenide, and ditolyldiselenide. Non-limiting examples of halogenated aromatic selenidesinclude pentachlorophenyl diselenide; pentafluorophenyl diselenide, and4-bromophenyl diselenide.

Another group of suitable additives are inorganic-selenium compounds,which may or may not contain carbon atoms (i.e., Se-containing compoundshaving at least one covalent and/or ionic bond between a Se atom and anon-carbon atom like O, N, P, Si, metals and the like, but do not haveSe—C covalent bonds). Non-limiting examples of inorganic-seleniumcompounds include selenium dioxide, and selenium dichloride. Anon-limiting example of a carbon-containing inorganic-selenium compoundis triphenylphosphine selenide.

Another group of suitable additives are organotellurium compounds,including organic tellurides (e.g., ditellurides), organotellurylhalides, and aromatic tellurocompounds (e.g., (di)aryltellurocompounds), preferably aromatic tellurides, more preferably withthe aromatic structure substituted with one or more EWG disclosedherein, and most preferably halogenated aromatic tellurides.Non-limiting examples of aromatic tellurides include diphenylditelluride; phenyl telluride, and ditolyl ditelluride. Non-limitingexamples of halogenated aromatic tellurides include pentachlorophenylditelluride; pentafluorophenyl ditelluride, and 4-bromophenylditelluride.

Another group of suitable additives are inorganic-tellurium compounds,which may or may not contain carbon atoms (i.e., Te-containing compoundshaving at least one covalent and/or ionic bond between a Te atom and anon-carbon atom like O, N, P, Si, metals and the like, but do not haveTe—C covalent bonds). Non-limiting examples of inorganic-telluriumcompounds include tellurium dioxide, and tellurium dichloride.Non-limiting examples of carbon-containing inorganic-tellurium compoundincludes triphenylphosphine tellurium, and tellurium dichloride complexwith thiourea.

Another group of suitable additives are organometallic coordinationcompounds, including unsaturated organometallic coordination compounds,and may be cyclic or acyclic. Non-limiting examples of cyclicorganometallic coordination compounds include bicyclo[2.2.1]hepta-2,5-diene-rhodium(I) chloride dimer;(bicyclo[2.2.1]hepta-2,5-diene)dichlororuthenium (II) polymer;bis(cyclopentadienyl)zirconium dichloride;bis(cyclopentadienyl)zirconium chloride hydride, and cyclopentadienyltitanium (IV) trichloride. Non-limiting examples of acyclicorganometallic coordination compounds include2,6,10-dodecatriene-1,12-diyl nickeltrifluoroacetic acid;2,6,10-dodecatriene-1,12-diyl nickelfluoroacetate, and bis(π-allylnickel trifluoroacetate).

Another group of suitable additives are aromatic iodonium compounds(e.g., aromatic iodonium salts), preferably aromatic iodonium halides,optionally having the aromatic structure substituted with one or moreEWG described herein. Non-limiting examples of aromatic iodoniumcompounds include diphenyl iodonium iodide; diphenyl iodonium bromide;diphenyl chloride; diphenyl iodonium nitrate; diphenyl iodonium acetate;diphenyl iodonium perchlorate; diphenyl iodonium9,10-dimethoxyanthracene-2-sulfonate; diphenyl iodoniumhexafluorophosphate; diphenyl iodonium perfluoro-1-butanesulfonate;diphenyl iodonium p-toluenesulfonate; diphenyl iodonium triflate, anddiphenyl iodonium-2-carboxylate monohydrate.

Another group of suitable additives are thiocyanate salts. Non-limitingexamples of thiocyanate salts include ammonium thiocyanate, and sodiumthiocyanate.

Another group of suitable additives are benzofurazans including, but notlimited to benzofuroxan; benzofurazan dioxide, and benzofurazan.

Another group of suitable additives are Verkade Superbases including butnot limited to trimethylphosphatrane; triisopropylphosphatrane, andtriisobutylphosphatrane.

Another group of suitable additives are acylhalides. Non-limitingexamples of acylchlorides include oxalylchloride; benzoyl chloride, andpentafluorobenzoyl chloride.

Other suitable additives include iodine; chlorosulfonated polyethylenerubber; poly(4-vinylpyridinium dichromate), crosslinked with 2% DVB;tetraphenyl tin; titanium isopropoxide; xanthone, andtris(triphenylphosphine)ruthenium hydrochloride.

Another group of suitable additives are amino acids and theirderivatives [e.g., aliphatic amino acids, aromatic amino acids,halogenated amino acids, amides thereof (e.g., corresponding cyclicamides, if any, and addition products with hydroxyl-containingcompounds), peptides thereof (e.g., with one or more other amino acids,including polypeptides), conjugates thereof (e.g., S-conjugates,Se-conjugates, Te-conjugates, disulfides, diselenides, ditellurides,selenylsulfides, tellurylsulfides, tellurylselenides), esters thereof(e.g., alkyls like methyl and ethyl, cycloalkyl, aryl), salts thereof(including those having metal cations, organometallic cations, andnon-metal cations, examples of which are disclosed herein), and variousisomers thereof having amine and acid groups], particularly sulfoaminoacids (preferably other than cystine), selenoamino acids, andtelluroamino acids.

Non-limiting examples of sulfoamino acids include cysteine,S-alk(en)ylcysteines (e.g., S-methylcysteine, S-ethylcysteine,S-propylcysteine, S-butylcysteine, S-t-butylcysteine, S-allylcysteine),γ-glutamyl-S-alk(en)ylcysteines (e.g., γ-glutamyl-S-methylcysteine,γ-glutamyl-S-propylcysteine, γ-glutamyl-S-allylcysteine),S-alk(en)ylcysteine sulfoxides (e.g., methiin, ethiin, propiin,S-butylcysteine sulfoxide, alliin, isoalliin,S-(methylthiomethyl)cysteine sulfoxide), S-arylcysteines (e.g.,S-benzylcysteine, S-phenylcysteine), halogenated sulfoamino acids (e.g.,S-(p-chlorobenzyl)cysteine, S-(p-bromophenyl)mercapturic acid,trifluoromethionine), petiveriin, 2- hydroxyethylcysteine,hydroxyethiin, S-allylmercaptocysteine, S-allylsulfonylalanine,N-acetyl-cysteine (mercapturic acid), penicillamine,(3,3-dimethylcysteine), S-[2-(4-pyridyl)ethyl]cysteine,S-(carboxymethyl)cysteine, S-nitrosoglutathione,S-nitroso-N-acetyl-penicillamine, S-benzylcysteine p-nitroanilide,S-[N-(3-phenylpropyl)(thiocarbamoyl)]cysteine,S-[N-benzyl(thiocarbamoyl)]cysteine, S-tritylcysteine,S-(t-butylthio)cysteine, cysteine-S-sulfate, cysteine-glutathionedisulfide, cysteinesulfinic acid, N,S-(dibenzyloxycarbonyl)cysteine,S-(acetamidomethyl)cysteine, S-(p-methoxybenzyl)cysteine,S-(p-methylbenzyl)cysteine, S-(t-butylthio)cysteine,N-(2-nitrophenylsulfenyl)alanine,N-(2-nitrophenylsulfenyl)phenylalanine, methionine, methioninesulfoxide, methionine sulfone, methionine sulfoximine, methylmethionine,glycylmethionine, methionylmethionine, N-(2,4-dinitrophenyl)methionine,N-(2,4-dinitrophenyl)methionine sulfone, N-benzoylmethionine,N-(benzyloxycarbonyl)methionine, N-formylmethionine,N-phthaloylmethionine, ethionine, ethionine sulfoxide, ethioninesulfone, ethionine sulfoximine, prothionine, prothionin sulfoximine,buthionine, buthionine sulfoxide, buthionine sulfone, buthioninesulfoximine, buthionin sulfoxime, glutathione, S-hexylglutathione,S-nitrosoglutathione, diglutathione, lanthionine, penthionine,cysteinylglycine, glutamylcysteine, glutamylcysteinylglycine,S-adenosylmethionine, homocystine, homocysteine,S-(2-amino-2-carboxyethyl)homocysteine, S-adenosylhomocysteine,homocysteinethiolactone, homocysteine sulfinic acid, homocysteic acid,S-phenylhomocysteine, N-acetyl-methionine, pentachloroanilinemercapturic acid, malonocysteine, conjugate of pentachlorothiophenol(PCTP) with cysteine, conjugate of PCTP with malonocysteine, conjugateof PCTP with pyruvate, conjugate of PCTP with acetate, conjugates ofPCTP with S-glycosides, conjugate of PCTP with glutamylcysteine,S-(pentachlorophenyl)cysteine, cysteic acid, cysteine sulfinic acid,cysteic acid monohydrate, methionine sulfone, methionine sulfoxide,propionine, 4-amino-2-methylthio-5-thiazolecarboxylic acid, [14C,15N]-2-amino-6-(methylthio)caproic acid,1-amino-3-(methylthio)propylphosphonic acid,1-amino-3-(methylthio)propylphosphinic acid,(4-amino-2-methyl-5-pyrimidinyl methylthio)acetic acid,4-(2′-carboxy-2′-hydroxy-ethylthio)-2-piperidinecarboxylic acid,aminomercaptobenoic acids (e.g., 3-amino-2-mercaptobenzoic acid,4-amino-3-mercapto benzoic acid) and derivatives thereof (e.g., thosedisclosed in U.S. Pat. No. 5,847,147, the entirety of which isincorporated herein by refererence), 2-aminohexanoic acid,4-amino-2-(ethylthio)-5-pyrimidinecarboxylic acid,2-amino-5-(2-propylthio)-1-pentanoic acid,2-amino-3-mercapto-3-methylbutanoic acid, 2-mercapto-4 methyl-5-thiazoleacetic acid, α-amino-β-mercapto-β,β-pentamethylenepropionic acid,6-amino-2-mercapto-5-methylpyrimidine-4-carboxylic acid, and theirderivatives.

Non-limiting examples of selenoamino acids include selenocysteine,Se-alk(en)ylselenocysteines (e.g., Se-methylselenocysteine,Se-propylselenocysteine, Se-allylselenocysteine,Se-propenylselenocysteine, Se-2-methyl-2-propenylselenocysteine),γ-glutamyl-Se-alk(en)ylselenocysteines (e.g.,γ-glutamyl-Se-methylselenocysteine, γ-glutamyl-Se-propylselenocysteine,γ-glutamyl-Se-allylselenocysteine), Se-alk(en)ylselenocysteineselenoxides (e.g., Se-proponylselenocysteine selenoxide),Se-propynylselenocysteine, Se-arylselenocysteines (e.g.,Se-benzylselenocysteine, Se-phenylselenocysteine),Se-phenylselenohomocysteine, halogenated selenoamino acids (e.g.,Se-(p-chlorobenzyl)selenocysteine), Se-allylselenocysteine,(Se,Se-dimethylselenocysteine), Se-(carboxymethyl)selenocysteine,selenoglutathione, selenodiglutathione, selenocysteine-cysteineselenylsulfide, selenocysteine-glutathione selenylsulfide,selenocysteine selenol, selenocysteine selenic acid, selenocysteineselenenic acid, Se-(p-methoxybenzyl)selenocysteine,Se-(p-methylbenzyl)selenocysteine, Se-n-butylselenocysteine,selenocystine, selenocystamine, sulfoselenocystine,N-tert-butoxycarbonyl-selenocystine,selenocystine-Se-methylselenocysteine, selenocystathionine,selenotrisulfides of cystine, selenocysteic acid, selenomethionine,selenomethionine selenoxide, selenomethionine selenone,Se-methylselenomethionine, Se-adenosylselenomethionine, selenoethionine,γ-glutamyl-selenoethionine, selenoglutathione, selenodiglutathione,selenolanthionine, γ-glutamyl-selenocysteinylglycine diselenide,selenohomocystine, selenohomocysteine, Se-adenosylselenohomocysteine,selenogammaaminobutyric acid, and seleninoalanine.

Non-limiting examples of telluroamino acids include tellurocysteine,tellurocystine, telluromethionine, aromatic telluroamino acids (e.g.,Te-phenyltellurohomocysteine, Te-phenyltellurocysteine), and halogenatedtelluroamino acids.

Another group of additives are boron-containing compounds, which may besubstituted or un-substituted (e.g., non-halogenated or(per)halogenated), and include, without limitation, boranes (e.g.,monoorgano-, diorgano-, and triorgano-borane compounds of or containingBR₃), borates (including boric acids, like B(OR)₃, as well assulfur-substituted borates and amine borate esters B(OR″)₃N), boronates(including boronic acids, like R′B(OR)₂, as well as functional boronatesYR″B(OR)₂ and diboronates Y′[R″B(OR)₂]₂), borinates (including borinicacids, like R′₂B(OR)), dioxaborolanes, dioxaborinanes, and metal andnon-metal salts thereof (including salts containing tetraorgano-boraneanions R₄B^(⊖)), where R and R′ are the same or different monovalentradicals chosen from H and linear, branched, and/or cyclic radicalshaving 40 or less (e.g., 1-20, 1-10, 1-8, 1-6, or 1-3) carbon atoms(e.g, alk(en)yl, aryl, aralk(en)yl, alk(en)aryl like alk(en)ylphenyl,cycloalk(en)yl, alk(en)ylcycloalk(en)yl, cycloalk(en)ylalk(en)yl, andcombinations thereof), optionally having one or more heteroatoms (e.g,O, N, S, P, Si), optionally substituted with one or more EWG asdisclosed above; R″ is the same or different divalent radicals chosenfrom linear, branched, and/or cyclic radicals having 20 or less carbonatoms (e.g, C₁₋₁₅ or C₁₋₃ alk(en)ylene, C₆₋₁₀ (alkyl)arylene, C₆₋₁₀(alkyl)cycloalk(en)ylene, and combinations thereof), optionally havingone or more heteroatoms, optionally substituted with one or more EWG asdisclosed above; Y is a functional group chosen from AZ as disclosedabove, thiocyano (—SCN), epoxyl, glycidyl, epithio, vinyl, allyl, andamines (primary or secondary); and Y′ is a divalent radical chosen frompolysulfide S_(y) or polyselenium Se_(y), where y is an integer of 1, 2,3, 4, and up to 8. Preferably, one or more of the carbons forming theC—O—B linkages are secondary and/or tertiary carbons so as to stericallyhinder hydrolysis. Boron-containing compounds may be used with orwithout amine-based compounds, such as those disclosed herein.

Non-limiting examples of boranes include triphenylphosphineborane,dibutoxyvinylborane, decaborane, morpholineborane, dichlorophenylborane,dibromophenylborane, tris(2,4,6-trimethylphenyl)borane). Salts ofboranes include metal salts (e.g., with cations of Na, Li, K, Mg, Zn,Co, Ca) and non-metal salts (e.g., with cations of quaternary ammonium,quaternary pyridinium, quaternary quinolinium, (organo)phosphonium,(organo)sulfonium, (organo)oxonium, (organo)iodonium, (organo)azonium,like tetrabutylammonium, tetramethylammonium, tetraethylammonium,tributylamine, triethanolamine, methylpyridinium, ethylpyridinium,butylpyridinium, methylquinolinium, ethylquinolinium, butylquinolinium)having an anion of R₄B^(⊖). At least one R in the anion may be an aryl,aralkyl, or alkaryl group, optionally having one or more substituents(e.g., EWG as disclosed above, linear or branched C₁₋₆ alkyls, EWG- ornon-EWG-substitued alkyls, phenyl, EWG- or non-EWG-substituted phenyl).The remaining R in the anion may be the same or different groups chosenfrom alk(en)yls, aryls, aralkyls, alk(en)aryls, cycloalk(en)yls,optionally having one or more substituents as disclosed above.Non-limiting examples of the anion include those having one aryl group(e.g., trialkylphenylboron, trialkyl(p-chlorophenyl)boron,trialkyl(p-fluorophenyl)boron,trialkyl(3,5-bistrifluoromethyl)phenylboron,trialkyl[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron,trialkyl(p-nitrophenyl)boron, trialkyl(m-nitrophenyl)boron,trialkyl(p-butylphenyl)boron, trialkyl(m-butylphenyl)boron,trialkyl(p-butyloxyphenyl)boron, trialkyl(m-butyloxyphenyl)boron,trialkyl(p-octyloxyphenyl)boron, trialkyl(m-octyloxyphenyl)boron), thosehaving two aryl group (e.g., dialkyldiphenylboron,dialkyldi(p-chlorophenyl)boron, dialkyldi(p-fluorophenyl)boron,dialkyldi(3,5-bistrifluoromethyl)phenylboron,dialkyldi[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron,dialkyl(p-nitrophenyl)boron, dialkyldi(m-nitrophenyl)boron,dialkyldi(p-butylphenyl)boron, dialkyldi(m-butylphenyl)boron,dialkyldi(p-butyloxyphenyl)boron, dialkyldi(m-butyloxyphenyl)boron,dialkyldi(p-octyloxyphenyl)boron, dialkyldi(m-octyloxyphenyl)boron),those having three aryl groups (e.g., monoalkyltriphenylboron,monoalkyltris(p-chlorophenyl)boron, monoalkyltris(p-fluorophenyl)boron,monoalkyltris(3,5-bistrifluoromethyl)phenylboron,monoalkyltris[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron,monoalkyltris(p-nitrophenyl)boron, monoalkyltris(m-nitrophenyl)boron,monoalkyltris(p-butylphenyl)boron, monoalkyltris(m-butylphenyl)boron,monoalkyltris(p-butyloxyphenyl)boron,monoalkyltris(m-butyloxyphenyl)boron,monoalkyltris(p-octyloxyphenyl)boron,monoalkyltris(m-octyloxyphenyl)boron), those having four aryl groups(e.g., tetraphenylboron, tetrakis(p-chlorophenyl)boron,tetrakis(p-fluorophenyl)boron,tetrakis(3,5-bistrifluoromethyl)phenylboron,tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron,tetrakis(p-nitrophenyl)boron, tetrakis(m-nitrophenyl)boron,tetrakis(p-butylphenyl)boron, tetrakis(m-butylphenyl)boron,tetrakis(p-butyloxyphenyl)boron, tetrakis(m-butyloxyphenyl)boron,tetrakis(p-octyloxyphenyl)boron, tetrakis(m-octyloxyphenyl)boron), wherethe alkyl group is linear or branched C₁₋₂₀ alkyls (e.g., n-butyl,n-octyl, n-dodecyl), and salts thereof (e.g., tetraphenylboron sodium).

Non-limiting examples of borates include alkylborates (e.g.,trimethylborate, triethylborate, tris(2-chloroethyl)borate,tris(2-aminoethyl)borate, tri(n-propyl)borate, triisopropylborate,tri(n-butyl)borate, triisobutylborate, tri(sec-butyl)borate,tri(t-butyl)borate, tri(n-pentyl)borate, trihexylborate,tris(4-methyl-2-pentyl)borate, tris(2-ethylhexyl)borate, trioctylborate,tris(1-methylheptyl)borate, tris(2-ethylhexyl)borate,tris(2,6-dimethyl-4-heptyl)borate, tris(diisopropylcarbinyl)borate,bis(diisobutylcarbinyl)borate, tris(3,5-dimethyl-4-heptyl)borate,tridecylborate, tridodecylborate, trioctadecylborate,tris(2-dimethylaminoethyl)borate); cycloalkylborates (e.g.,tricyclohexylborate, tri(2-cyclohexylcyclohexyl)borate,di(n-butyl)[2,6-di(t-butyl)-4-methylphenyl]borate); (alkyl)arylborates(e.g., triphenylborate, tri(o-tolyl)borate, tri(m,p-cresyl)borate,tri(o-chlorophenyl)borate, tri(nonylphenyl)borate, dihydrogennonylphenyl borate); alkenylborates (e.g., triallylborate); cyclicesters of boric acid (e.g., glycerol borate, triethylamine glycerolborate, monoethanolamine glycerol borate, triethanolamine borate(boratran), tripropanolamine borate, triisopropanolamine borate, andthose formed form alkanolamines, alkane polyols, and cycloalkanepolyols, such as propane-1,3-diol, phenyl ethane-1,2-diol,ethyl-2,4-dimethylpentane-2,4-diol, and 2-ethyl-2hydroxymethyl-1,3-propane diol); inorganic borates (e.g., sodiumtetraborate, lithium tetraborate); and adducts of amines (e.g., tertiaryalkyl primary amines, and those disclosed herein) with borates (e.g.,boro-tetra-n-propylate, tri(n-propyl)borate, and those disclosed herein)and/or boranes (e.g., dimethylamine borane, pyridine borane,trimethylamine borane, triethylamine borane),trimethylamine-N-ethamidoborane,[bis(2-chloroethyl)amino]bis(o-hydroxyphenoxy)borane,tris[bis(2-chloroethyl)amino]borane, ethylenediamine bisborane,t-butylamine borane, hexamethylenetetramine borane,N,N-dimethylbenzylamine borane, tetrakis(dimethylamino)diborane.

Non-limiting examples of boronates and boronic acids include4-borono-benzoic acid, 3-ethoxycarbonylphenylboronic acid,3-isopropoxycarbonylphenylboronic acid, m-nitrophenylboronic acid,p-bromophenylboronic acid, p-chlorophenylboronic acid, m- orp-benzenediboronic acid, nonylboronic acid, o-phenylene-benzeneboronate,2,2′-stilbenediboronic acid, p-tolylboronic acid, phenylboronic acid,1-naphthaleneboronic acid, 1-hexaneboronic acid, 1-propaneboronic acid,1-pentaneboronic acid, ferroceneboronic acid,(2-phenylthioethenyl)dibutylboronate, 2-mesityleneboronic acid,2,2′-dimethoxybiphenyl-5-boronic acid, 1-naphthaleneboronic acid,2-chloro-4-fluorophenylboronic acid,2-chloro-4-trifluoromethylphenylboronic acid,2-fluoro-4-iodophenylboronic acid, 2-methoxyphenylboronic acid,2-(methylthio)phenylboronic acid, 2-naphthaleneboronic acid,2-thiopheneboronic acid, tolylboronic acid, 3-carboxyphenylboronic acid,3-chlorophenylboronic acid, 3-chloro-4-fluorophenylboronic acid,3-fluorophenylboronic acid, 3-methoxyphenylboronic acid,3-(methylthio)phenylboronic acid, 3-tolylboronic acid,3-(trifluoromethyl)phenylboronic acid, 4-biphenylboronic acid,4-bromophenylboronic acid, 4-bromo-2,3-difluorophenylboronic acid,4-carboxyphenylboronic acid, 4-chlorophenylboronic acid,4-cyanophenylboronic acid, 4-fluorophenylboronic acid,4-fluoro-3-methylphenylboronic acid, 4-methoxyphenylboronic acid,4-(methylthio)phenylboronic acid, 4-tolylboronic acid,4-(trifluoromethoxy)phenylboronic acid, 5-fluoro-2-methylphenylboronicacid, 5-indolylboronic acid, 2,4-dichlorophenylboronic acid,2,4-difluorophenylboronic acid, 2,4-dimethylphenylboronic acid,3,4-dichlorophenylboronic acid, 3,4-difluorophenylboronic acid,3,4-dimethylphenylboronic acid, 3,5-bis(trifluoromethyl)phenylboronicacid, 3,5-dichlorophenylboronic acid, 3,5-difluorophenylboronic acid,3,4,5-trifluorophenylboronic acid.

Non-limiting example of heterocylic compounds having at least one boronatom as a ring member include dioxaboroles (e.g., catecholborane(1,3,2-benzodioxaborole), 2-(5,6-dichlorophenyl)-1,3,2-benzodioxaborole,2-(5,6-dichloro-4-methylthiophenyl)-1,3,2-benzodioxaborole,2,4,5-triphenyl-1,3,2-dioxaborole); dioxaborlanes (e.g.,2-methoxy-1,3,2-dioxaborolane,2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,4-hydroxymethyl-1,3,2-dioxaborolan-2-ol,(2-isopropoxy-1,3,2-dioxaborolan-4-yl)methanol,[2-(4-hydroxymethyl-1,3,2-dioxaborolan-2-yloxy)-1,3,2-dioxaborolan-4-yl]methanol,bispinacolatobiborate, 2-bis(2-choroethyl)amino-1,3,2-dioxaborolane,[2-1,3,2-dioxaborolan-2-yloxy)ethyl]dimethylamine,[2-(4,4,5,5,-tetramethyl-1,3,2-dioxaborolan-2-yloxy)ethyl]dimethylamine,2,7-di(ethylaminomethyl)-2,4,6,9-tetraoxa-5-bora-spiro[4,4]nonane,2,7-di(t-butylaminomethyl)-2,4,6,9-tetraoxa-5-bora-spiro[4,4]nonane);dioxaborinanes (e.g., tripropyleneglycol biborate, dibutyleneglycolbiborate, tributyleneglycol biborate, hexyleneglycol biborate,trihexyleneglycol biborate, 1,2-dioxaborinane,2-butyl-1,3,2-dioxaborinane, 1,3,2-dioxaborinan-2-ol,4-methyl-1,3,2-dioxaborinan-2-ol,4,4,6-trimethyl-1,3,2-dioxaborinan-2-ol,2-isopropoxy-1,3,2-dioxaborinane,2-isopropoxy-4-methyl-1,3,2-dioxaborinane,2-isopropoxy-4,4,6-trimethyl-1,3,2-dioxaborinane,2-bis(2-chloroethyl)amino-1,3,2-dioxaborinane,[2-(1,3,2-dioxaborinan-2-yloxy)ethyl]dimethylamine,[2-(4-methyl-1,3,2-dioxaborinan-2-yloxy)ethyl]dimethylamine,[2-(4,4,6-trimethyl-1,3,2-dioxaborinan-2-yloxy)ethyl]dimethylamine,2,2′-bis(5,5-dimethyl-1,3,2-dioxaborinane), 2,2′-oxybis(1,3,2-dioxaborinane), 2,2′-oxybis(4,4,6-trimethyl-1,3,2-dioxaborinane),2,2′-(methyltrimethylenedioxy)bis(4-methyl-1,3,2-dioxaborinane),5-methyl-5-propyl-2-(p-tolyl)-1,3,2-dioxaborinane,2-hydroxy-4,4,6-trimethyl-1,3,2-dioxaborinane); dithiaborolanes (e.g.,2-methyl-dithiaborolane, 2-methylthio-dithiaborolane,2-chloro-dithiaborolane); dithiaborinanes (e.g.,2-chloro-1,3,2-dithiaborinane,2-bis(2-chloroethyl)amino-1,3,2-dithiaborinane); boroxins (e.g.,boroxin, tributylboroxin, trimethoxyboroxin, triphenylboroxin,tris(cyclohexyloxy)boroxin); borazines (e.g., borazine,trimethylborazine, 2,4,6-trichloroborazine,2,4,6-trimethyl-1,3,5-triphenylborazine).

Other boron-containing compounds include boron-containing organosulfides(e.g., B-nonyl-bis(octylphenol)sulfide), borinates (e.g.,o-(2-aminoethyl)diphenylborinate), as well as metal salts and non-metalsalts of boron complexes (e.g., dipentylammonium tetrafluoroborate,dibutylammonium tetrafluoroborate, sodium tetraethyoxyborate, sodiumtetraisopropoxyborate, trityl tetrafluoroborate, ammonia boron fluoride,cetyltrimethylammonium borohydride, methyltrioctylammonium borohydride,tetraethylammonium borohydride, sodium borofluoride, tetrapropylammoniumtetrafluoroborate, triphenylsulfonium tetrafluoroborate,diphenyliodonium tetrafluoroborate, tri(p-tolyl)sulfoniumtetrafluoroborate, rubidium tetrafluoroborate, mono-N-butylammoniumtetrafluoroborate, sodium tetramethoxyborate, sodium boroheptonate).

Another group of additives are Si-containing compounds, which include,without limitation, those having the structures R_(x)SiR′_(4−x) orS_(y)[(R″)_(z)G]₂, where R is the same or different monovalent radicalschosen from H, halogen (e.g., F, Cl, Br, I), linear or branched C₁₋₈ orC₂₋₄ alkyl, aryl, aralkyl, and vinyl, R′ is the same or differentmonovalent radical chosen from halogen, hydroxyl, linear or branchedC₁₋₈ or C₂₋₄ oxyalkyl, C₅₋₁₀ oxycycloalkyl, oxyaryl, oxyaryalkyl, andoxyvinyl, R″ is the same or different divalent radicals, preferablylinear or branched C₁₋₁₈ divalent hydrocarbons, such as C₁₋₁₈ or C₂₋₄alkylenes, optioinally having one or more heteroatoms (e.g., O, N, S), Gis the same or different Si-containing monovalent radicals, such assubstituted or non-substituted (cyclo)(poly)(alkyl)siloxanes, or silylgroups of —Si(R_(x))(R′_(3−x)) where R and R′ are as described above, xis a whole number of 0, 1, 2, or 3, y is an integer of 1, 2, 3, or 4,and up to 8, and z is 0 or 1.

Non-limiting examples of oxyalkyl silanes include tetramethoxysilane,tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane,tetraoctylsilane, methyltrimethoxysilane, methyltriethoxysilane,methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,ethyltriisopropoxysilane, octyltrimethoxysilane, octyltriethoxysilane,vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane,phenyltriethoxysilane, trimethoxysilane, triethoxysilane,triisopropoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane,dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane,diethyldiethoxysilane, dimethoxysilane, diethoxysilane,difluorodimethoxysilane, difluorodiethoxysilane,trifluoromethyltrimethoxysilane, and trifluoromethyltriethoxysilane.

Non-limiting examples of halogenated silanes include trichlorosilane,tribromosilane, fluorotrichlorosilane, methyltribromosilane,ethyltrichlorosilane, chlorotrimethylsilane, fluorotrimethylsilane,vinyltrichlorosilane and phenyltrichlorosilane.

Non-limiting examples of sulfur-containing silicocompounds includedithiobis(pentamethylcyclotrisiloxane),3,3′-bis(trimethoxysilylpropyl)disulfide,3,3′-bis(triethoxysilylpropyl)disulfide,3,3′-bis(triethoxysilylpropyl)tetrasulfide,3,3′-bis(triethoxysilylpropyl)octasulfide,3,3′-bis(trimethoxysilylpropyl)tetrasulfide,2,2′-bis(triethoxysilylethyl)tetrasulfide,3,3′-bis(trimethoxysilylpropyl)trisulfide,3,3′-bis(triethoxysilylpropyl)trisulfide,3,3′-bis(tributoxysilylpropyl)disulfide,3,3′-bis(trimethoxysilylpropyl)hexasulfide,3,3′-bis(trimethoxysilylpropyl)octasulfide,3,3′-bis(trioctoxysilylpropyl)tetrasulfide,3,3′-bis(trihexoxysilylpropyl)disulfide,3,3′-bis(tri-2″-ethylhexoxysilylpropyl)trisulfide,3,3′-bis(triisooctoxysilylpropyl)tetrasulfide,3,3′-bis(tri-t-butoxysilylpropyl)disulfide,2,2′-bis(methoxydiethoxysilylethyl)tetrasulfide,2,2′-bis(tripropoxysilylethyl)pentasulfide,3,3′-bis(tricyclohexoxysilylpropyl)tetrasulfide,3,3′-bis(tricyclopentoxysilylpropyl)trisulfide,2,2′-bis(tri-2′-methylcyclohexoxysilylethyl)tetrasulfide,bis(trimethoxysilylmethyl)tetrasulfide,3-methoxyethoxypropoxysilylpropyl-3′-diethoxybutoxysilylpropyl-tetrasulfide,2,2′-bis(dimethylmethoxysilylethyl)disulfide,2,2′-bis(dimethyl-sec-butoxysilylethyl)trisulfide,3,3′-bis(methylbutylethoxysilylpropyl)tetrasulfide,3,3′-bis(di-t-butylmethoxysilylpropyl)tetrasulfide,2,2′-bis(phenylmethylmethoxysilylethyl)trisulfide,3,3′-bis(diphenylisopropoxysilylpropyl)tetrasulfide,3,3′-bis(diphenylcyclohexoxysilylpropyl)-disulfide,3,3′-bis(dimethyl-ethylmercapto-silylpropyl)tetrasulfide,2,2′-bis(methyldimethoxysilyl-ethyl)trisulfide,2,2′-bis(methyl-ethoxypropoxysilylethyl) tetrasulfide,3,3′-bis(diethylmethoxysilylpropyl) tetrasulfide,3,3′-bis(ethyl-di-sec-butoxysilylpropyl)disulfide,3,3′-bis(propyldiethoxysilylpropyl)disulfide,3,3′-bis(butyldimethoxysilylpropyl)trisulfide,3,3′-bis(phenyldimethoxysilylpropyl)tetrasulfide,3-phenylethoxybutoxysilylpropyl-3′-trimethoxysilylpropyl-tetrasulfide,4,4′-bis(trimethoxysilylbutyl)tetrasulfide,6,6′-bis(triethoxysilylhexyl)tetrasulfide,12,12′-bis(triisopropoxysilyldodecyl)disulfide,18,18′-bis(trimethoxysilyloctadecyl)tetrasulfide,18,18′-bis(tripropoxysilyloctadecenyl)tetrasulfide,4,4′-bis(trimethoxysilyl-buten-2-yl)tetrasulfide,4,4′-bis(trimethoxysilylcyclohexylene)tetrasulfide,5,5′-bis(methyldimethoxysilylpentyl)trisulfide,3,3′-bis(trimethoxysilyl-2-methylpropyl)tetrasulfide,3,3′-bis(phenyldimethoxysilyl-2-methylpropyl)disulfide.

Another group of additives are crosslinkable and/or polymerizablecompounds (e.g., monomers, and oligomers and polymers formed from suchmonomers) having one, two, three, or more unsaturated moieties eachhaving at least one readily extractable hydrogen in the α position tothe unsaturated bonds (e.g., vinyl group, allyl group, isopropenylgroup, acryloyl group, methacryloyl group, acrylamide group,methacrylamide group). Such additives may be acidic (includinganhydrides thereof) or non-acidic, being sulfur-free or comprising oneor more heteroatoms (e.g., O, N, S, P, Si), being aliphatic, alicyclic,or aromatic, and include mono-, di-, and poly-esters, mono-, di-, andpoly-amides, mono-, di-, and poly-esteramides, bismaleimides, organicsalts (e.g., the cations being (organo)ammoniums) and metallic salts(e.g., the cations being Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ti, Zr, Cr,Mo, Mn, Fe, Ru, Co, Rh, Ir, Cu, Zn, Cd, Al) thereof, and liquid vinylpolydienes.

Acidic crosslinkable and/or polymerizable compounds may have one or moreacidic moieties chosen from carboxyl group, sulfonico group, sulfinicogroup, phosphono group, phosphinico group, and acid anhydride radical,include, without limitation, acrylic acid, methacrylic acid, ethacrylicacid, propylacrylic acid, other alkylacrylic acids, the mono- orpoly-unsaturated fatty acids and polyacids as described in U.S.application No. 10/859,537, the disclosure of which is incorporatedherein by reference, and anhydrides thereof. Non-limiting examples ofacidic organosulfur compounds and acidic organophosphorous compoundsinclude vinylsulfonic acid, vinylphosphonic acid.

One group of acidic crosslinkable and/or polymerizable compounds mayhave a structure of [X(L)_(p)R]_(m)[(L)_(q)A]_(n), where X is the sameor different monovalent radicals that are crosslinkable and/orpolymerizable; L is the same or different divalent radicals, preferably—COO— or —CONH—; R is the same or different radicals having a valency of2, 3, or 4, and up to 6, comprising 1 to 30 carbon atoms, optionallycomprising ether, ester, and/or amide linkages; A is the same ordifferent monovalent acidic radicals or divalent acidic radicals; m andn are integers independently chosen from 1, 2, 3, 4, and up to 8, withm+n being 2, 3, or 4, and up to 10; p is the same or different numbersof 0 or 1; and q is the same or different numbers of 0 or 1.Non-limiting examples of X include linear, branched, or cyclic C₂₋₁₀alkenyls, such as vinyl, allyl, isoallyl, propenyl, and isopropenyl.Non-limiting examples of R include —CH₂—, —(CH₂)₂—, —(CH₂)₄—, —(CH₂)₆—,—(CH₂)₈—, —(CH₂)₁₀—, —(CH₂)₂₀—, —(CH₂)₂O(CH₂)₂—, —(CH₂)₂O[O(CH₂)₂]₂—,—(CH₂)₂OCO(CH₂)₂COO(CH₂)₃—, —(CH₂)₂O[O(CH₂)₂]₆—,

(x, y, and z are independent whole numbers of 0, 1, 2, and up to 10, andx+y+z is an averaged number of 1 or greater, or 3.5 or greater), andcombinations of 2 or more thereof. Non-limiting examples of A include—COOH, —CH(COOH)₂, —SO₃H, —OPO₃H₂, ═(O₂)PO₂H (i.e.,

—C₆H₃(COOH)₂

and combinations of two or more thereof.

Non-limiting examples of acidic compounds with the above-describedstructure include CH₂═C(R)CONH(CH₂)₂COOH, CH₂═C(R)CONH(CH₂)₁₀CH(COOH)₂,CH₂═CHC₆H₄CH₂COOH, CH₂═C(R)COO(CH₂)₈CH(COOH)₂,CH₂═C(R)COO(CH₂)₁₀CH(COOH)₂, CH₂═CHC₆H₄COOH, CH₂═C(R)CONH(CH₂)₂OPO₃H₂,CH₂═C(R)COO(CH₂)₁₂CH(COOH)₂, CH₂═CH₆H₄(CH₂)₂COOH,CH₂═C(R)COO(CH₂)₂OCOC₆H₃(COOH)₂, CH₂═C(R)COO(CH₂)₂OPO₃H₂,CH₂═CHC₆H₄SO₃H, CH₂═C(R)COO(CH₂)₂OCOC₈H₄O₃, CH₂═C(R)COO(CH₂)₂OP(O₂H)OPh,CH₂═CHC₆H₄CH₂SO₃H, [CH₂═C(R)COO(CH₂)₂O]₂CHOCOC₆H₃(COOH)₂,[CH₂═C(R)COO(CH₂)₂O]₃COCOC₆H₃(COOH)₂,CH₂═C(R)COO(CH₂)₂OCO(CH₂)₂COOCH₂CH[CH2OCOC(R)═CH₂]OCOC₆H₃(COOH)₂,[CH₂═C(R)COOCH₂CH[OCOC₆H₃(COOH)₂]CH₂OCH₂]₂, CH₂═C(R)CONHC(CH₃)₂CH₂SO₃H,[CH₂═C(R)COO(CH₂)₂O]₂C[CH₂OCOC₆H₃(COOH)₂]₂, CH₂═C(R)COOC(CH₃)₂CH₂SO₃H,[CH₂═C(R)COO(CH₂)₂O]₂PO₂H, CH₂═C(R)CONH(CH₂)₂SO₃H,CH₂═C(R)COO(CH₂)₁₀SO₃H, CH₂═C(R)COO(CH₂)₂SO₃H, CH₂═C(R)COO(CH₂)₆SO₃H,CH₂═C(R)CONHC₆H₄SO₃H, CH₂═C(R)COOC₆H₄SO₃H,

and combinations of two or more thereof (e.g., combinations ofP-containing acidic compounds and carboxyl-containing acidic compounds).

Salts of the acidic compounds described above are another group ofcrosslinkable and/or polymerizable compounds. Suitable cations of suchsalts include any and all of those disclosed herein, such as metalcations and amine-based cations. Metal salts may be derived by reactingthe acidic compounds with monovalent and/or divalent metal oxides. Othersalts include, for example, reaction products of divalent metal oxidewith a) mono-basic unsaturated carboxylic acids such as acrylic acidand/or methacrylic acid and/or b) di-basic and/or polybasic carboxylicacids having mono- or polyunsaturation, and/or anhydrides thereof, suchas those described in U.S. Pat. No. 6,566,483, the entire disclosure ofwhich is incorporated herein by reference. Non-limiting examples includezinc diacrylthioic acid.

Acidic compounds described herein can be condensed with polyamines(forming polyamides), polyols (forming polyesters), or aminoalcohols(forming esteramides) to form acidic or non-acidic polyfunctionalcrosslinkable and/or polymerizable compounds suitable for use in thecompositions of the present disclosure. Non-limiting examples ofunsaturated carboxylic acid condensates include ethyleneglycoldi(meth)acrylate, diethyleneglycol di(meth)acrylate, triethyleneglycoldi(meth)acrylate, tetraethyleneglycol di(meth)acrylate,nonaethyleneglycol di(meth)acrylate, polyethyleneglycoldi(meth)acrylate, propyleneglycol di(meth)acrylate, dipropyleneglycoldi(meth)acrylate, tripropyleneglycol di(meth)acrylate, neopentylglycoldi(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,9-nonanediol di(meth)acrylate, trimethylolpropanedi(meth)acrylate, trimethylolpropane tri(meth)acrylate, glyceryldi(meth)acrylate, glyceryl tri(meth)acrylate, pentaerythritoldi(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, urethane di(meth)acrylate, epoxy (meth)acrylate,bisphenol A diglycidylether diacrylate, allyl (meth)acrylate,2,2′-bis[4-(meth)acryloyloxyethoxyphenyl]propane,2,2′-bis[4-(meth)acryloyloxyethoxyethoxyphenyl]propane,2,2′-bis{4-[3-(meth)acryloyloxy-2-hydroxypropoxy]phenyl}propane.

Non-limiting example of bismaleimide include N,N′-m-phenylenedimaleimide(HVA-2, available from Dupont). Non-limiting examples of allyl estersinclude triallyl cyanurate (Akrosorb® 19203, available from AkrochemCorp. of Akron, Ohio), triallyl isocyanurate (Akrosorb® 19251, alsoavailable from Akrochem Corp.), and triallyl trimaletate (TATM,available from Sartomer Company of Exton, Pa.). Non-limiting examples ofmono- or polyunsaturated polycarboxylic acids and derivatives thereofinclude citraconic acid, itaconic acid, fumaric acid, maleic acid,mesaconic acid, aconitic acid, maleic anhydride, itaconic anhydride,citraconic anhydride, poly(meth)acrylic acid, polyitaconic acid,copolymers of (meth)acrylic acid and maleic acid, copolymers of(meth)acrylic acid and styrene, and fatty acids having a C₆ or longerchain, such as hexadecenedioic acid, octadecenedioic acid,vinyl-tetradecenedioic acid, eicosedienedioic acid,dimethyl-eicosedienedioic acid, 8-vinyl-10-octadecenedioic acid,anhydrides thereof, methyl, ethyl, and other linear or branched alkylesters thereof, amides thereof, esteramides thereof, and mixturesthereof.

Liquid vinyl polydienes are liquid at ambient temperature, such asliquid vinyl polybutadiene homopolymers and copolymers (e.g., having avinyl-1,2 content of at least 60%, or at least 65%), and can have low tomoderate viscosity, low volatility and emission, high boiling point(such as greater than 300° C.), and molecular weight of about 1,000 toabout 5,000, such as about 1,800 to about 4,000, or about 2,000 to about3,500. Non-limiting examples of liquid vinyl polydienes include highvinyl polybutadiene having a vinyl-1,2 content of 90% and a molecularweight of about 3,200, high vinyl polybutadiene having a vinyl-1,2content of 70% and a molecular weight of about 2,400, high vinylpoly(butadiene-styrene) copolymer having a vinyl-1,2 content of 70% anda molecular weight of about 2,400, and other liquid vinyl polymers asdisclosed herein above.

Another group of crosslinkable and/or polymerizable compounds isethylenically unsaturated organosulfur compounds, which may or may notcomprise one or more heterocyclic structures, and include, withoutlimitation, compounds having mercapto groups and tautomers thereof, suchas thiouracils, triazinedithions, and mercaptothiazoles. Genericstructures of such organosulfurs may include[X(Y)_(w)R(R_(s))_(x)]_(y)(S)_(z), where X is the same or differentmonovalent radicals that are crosslinkable and/or polymerizable; Y isthe same or different divalent radicals chosen from —COO—, —CH₂O—, and—C₆H₄CH₂O—; R is the same or different divalent; R_(s) is the same ordifferent sulfur-containing radicals; w is 0 or 1; x is 0 or 1; y is 1or 2; z is 0 or 1; and x+z=1. Non-limiting examples of X include linear,branched, or cyclic C₂₋₁₀ alkenyls, such as vinyl, allyl, isoallyl,propenyl, and isopropenyl. Non-limiting examples of R include—CH₂C₆H₄CH₂—, —(CH₂)₂O(CH₂)₂—, —C₆H₄CH₂—,—(CH₂)_(x)Si(CH₃)₂OSi(CH₃)₂(CH₂)_(y)— where x and y are the same ordifferent integers of 1 to 5, C₁₋₁₂ saturated hydrocarbons (such aslinear, branched, and/or cyclic alkylenes, like —(CH₂)₆—, —(CH₂)₁₀—,—(CH₂)₁₁—,

Non-limiting examples of R_(s) include

where R″ is H or C₁₋₆ alkyl,

Non-limiting examples of such organosulfurs include thioethers andpolysulfides of the above structures, and acryloxy-4-thiophenol, zincacryloxythiophenol, bis(4-acryloxybenzene)disulfide, diallyl disulfide,diallyl trisulfide, methyl allyl sulfide, pentachlorophenyl vinylsulfide, pentachlorophenyl vinyl sulfoxide,tetrachloro(vinylthio)benzenethiol. Other examples may have one of theorganosulfur structures disclosed herein above, wherein at least one ofthe substituents R₁ to R₅ (preferably R₂, R₃, and/or R₄) and/or at leastone of the substituents R₆ to R₁₀ (preferably R₇, R₈, and/or R₉) eachcomprises at least one crosslinkable and/or polymerizable radical X asdescribed above.

Aromatic crosslinkable and/or polymerizable compounds further includethose having the diaryl ether structure described above, wherein atleast one of the substituents R₁ to R₅ (preferably R₂, R₃, and/or R₄)and/or at least one of the substituents R₆ to R₁₀ (preferably R₇, R₈,and/or R₉) each comprises at least one crosslinkable and/orpolymerizable radical X as described above, and cinnamyl alcohol,cinnamic aldehyde, methoxycinnamic aldehyde, cinnamyl methyl ether,cinnamyl ethyl ether, cinnamyl allyl ether, cinnamyl phenyl ether,cinnamyl benzyl ether, cinnamyl naphthyl ether, cinnamyl methyl ketone,cinnamyl ethyl ketone, cinnamyl allyl ketone, cinnamyl phenyl ketone,cinnamyl benzyl ketone, cinnamyl acetate, cinnamyl propionate, cinnamylbutylate, cinnamyl benzoate, methyl cinnamate, methyl methylcinnamate,ethyl cinnamate, vinyl cinnamate, allyl cinnamate, phenyl cinnamate,benzyl cinnamate, cinnamyl cinnamate, naphthyl cinnamate, cinnamylmethyl carbonate, cinnamyl phenyl carbonate, allylbenzene, allyl phenylether, allyl benzoate, allyl phenylacetate.

Non-limting examples of other crosslinkable and/or polymerizablecompounds include styrene, α-methylstyrene, and derivatives thereof(e.g., p-chlorostyrene, p-hydroxystyrene, divinyl-benzene), fumaric acidesters (e.g., monomethyl fumarate, diethyl fumarate, diphenyl fumarate),allyl esters (e.g., diallyl phthalate, diallyl terephthalate, diallylcarbonate, allyl diglycol carbonate), epoxies (e.g., diglycerolpolyglycidyl ether, pentaerythritol polyglycidyl ether,1,4-bis(2,3-epoxypropoxyperfluoroisopropyl)cyclohexane, sorbitolpolyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinediglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycoldiglycidyl ether, phenyl glycidyl ether, p-t-butylphenyl glycidyl ether,adipic acid diglycidyl ether, o-phthalic acid diglycidyl ether,dibromophenyl glycidyl ether, 1,2,7,8-diepoxyoctane,4,4,′-bis(2,3-epoxypropoxyperfluoroisopropyl)diphenyl ether,3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate,3,4-epoxycyclohexyloxysilane, ethylene glycol-bis(3,4-epoxycyclohexanecarboxylate)), oxetanes (e.g., 3-ethyl-3-hydroxymethyloxetane,3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(naphthoxymethyl)oxetane,di[1-ethyl(3-oxetanyl)]methyl ether,3-ethyl-3-(2-ethylhexyl-oxymethyl)oxetane,1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene), vinyl ethers(e.g., vinyl 2-chloroethyl ether, vinyl n-butyl ether, triethyleneglycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether,trimethylolethane trivinyl ether, vinyl glycidyl ether), and silanes(e.g., γ-methacryloxypropyltrimethoxysilane,δ-methacryloxyoctyltrimethoxysilane, vinyltrimethoxysilane, and thosedescribed in co-owned and co-pending U.S. application Ser. No.10/120,012, now U.S. Publication No. 2003/0004013, the entirety of whichis incorporated herein by reference).

In one example, an additive, which serves at least as a crosslinkco-agent, includes a metal salt, such as a zinc salt or a magnesiumsalt, of an unsaturated acid having 3 to 8 carbon atoms, such as acrylicacid and methacrylic acid. Examples include, but are not limited to, oneor more metal salts of diacrylates, dimethacrylates, andmonomethacrylates, wherein the metal is magnesium, calcium, zinc,aluminum, sodium, lithium, or nickel. Preferred acrylates include zincacrylate, zinc diacrylate, zinc methacrylate, zinc dimethacrylate, andmixtures thereof. The crosslink co-agent is typically present in anamount greater than about 10 phr, preferably from about 20 phr to about40 phr, more preferably from about 25 phr to about 35 phr.

In another example, the additive serves to increase the CoR of the coreand/or the golf ball, and includes hypervalent iodines (e.g.,diphenyliodonium iodide), Se-containing compounds (e.g., diphenyldiselenide), Sn-containing compounds (e.g., diphenyltin dichloride), andsulfonamides (e.g., sulfamide). Some of these additives (e.g.,hypervalent iodines, Sn-containing compounds, and sulfonamides) may beused in amounts equal to or greater than that of the crosslinkinitiators (e.g., peroxides), with a weight ratio of the additive to thecrosslink initiator being 1:1 or greater, preferably 1.5:1 or greater,more preferably from 2:1 to 10:1, most preferably from 2:1 to 6:1.Alternatively, such additives may be used in amounts of 0.1 phr orgreater, preferably from 0.5 phr to 10 phr, more preferably from 1 phrto 5 phr, most preferably from 1.5 phr to 3 phr. Other additives (e.g.,Se-containing compounds) may be used in amounts less than that of thecrosslink initiators (e.g., peroxides), with a weight ratio of theadditive to the crosslink initiator being 0.5:1 or less, preferably from0.05:1 to 0.3:1, more preferably from 0.1:1 to 0.2:1. Alternatively,such additives may be used in amounts of 0.5 phr or less, preferablyfrom 0.05 phr to 0.5, more preferably from 0.1 phr to 0.3 phr, morepreferably from 0.15 phr to 0.3 phr.

Also useful in the core are isocyanate-containing compounds (e.g.,monomeric compounds like p-tolune sulfonyl isocyanate (PTSI fromVanDeMark Inc. of Lockport, N.Y.) and polymeric compounds like polymericmethylene diphenyl diisocyanate (PAPI® MDI from Dow Chemical)),oxazolidines, oxazolanes, orthoformates (e.g., trimethyl- and triethylorthoformates), orthoacetates (e.g., trimethyl- and triethylorthoacetates), vinyl silanes, solution-converted polybutadienes asdescribed in co-owned and co-pending U.S. application Ser. No.10/807,846, and metallic mercaptothiazoles and metallicmercaptobenzothiazoles as described in co-owned and co-pending U.S.application Ser. Nos. 10/437,386 and 10/437,387. The entire disclosuresof these applications are incorporated herein by reference.

Another group of additives are fillers, which may include materials suchas tungsten, zinc oxide, barium sulfate, silica, calcium carbonate, zinccarbonate, metals, metal oxides and salts, regrind (recycled corematerial typically ground to about 30 mesh particle),high-Mooney-viscosity rubber regrind, and the like. Fillers added to oneor more portions of the golf ball typically include processing aids orcompounds to affect rheological and mixing properties, density-modifyingfillers, tear strength, or reinforcement fillers, and the like. Thefillers may be inorganic, and include numerous metals or metal oxides,such as zinc oxide and tin oxide, as well as barium sulfate, zincsulfate, calcium carbonate, barium carbonate, clay, tungsten, tungstencarbide, an array of silicas (e.g., quartz, silica, silica-alumina,silica-titania, silica-zirconia, silica-magnesia, silica-calcia,silica-barium oxide, silica-strontium oxide, silica-titania-sodiumoxide, silica-titania-potassium oxide), titania, zirconia, alumina, andmixtures thereof. Fillers may also include various foaming agents orblowing agents which may be readily selected by one of ordinary skill inthe art. Fillers may include polymeric, ceramic, metal, and glassmicrospheres may be solid or hollow, and filled or unfilled. Organicfiller may include polymethyl methacrylate, polyethyl methacrylate,methyl methacrylate-ethyl methacrylate copolymer, ethylmethacrylate-butyl methacrylate copolymer, methylmethacrylate-trimethylolpropane methacrylate copolymer, polyvinylchloride, polystyrene, chlorinated polyethylene, nylon, polysulfone,polyethersulfone, and polycarbonate. Fillers are typically also added toone or more portions of the golf ball to modify the density thereof toconform to uniform golf ball standards. Fillers may also be used tomodify the weight of the center or at least one additional layer forspecialty balls, e.g., a lower weight ball is preferred for a playerhaving a low swing speed.

The additives disclosed herein may be used singly or as a combination oftwo or more thereof. The use of two or more additives chosen fromdifferent groups may independently or synergistically provide a singleor two or more desired effects. The amount of each additive, whenpresent in the composition, may be adjusted to optimize the desiredeffects. In one example, the amount is 0.1 phr to 5 phr by weight of thebase polymer in the composition.

The compositions described above may be used in any one or more golfball portions present in any construction, such as the inner center,inner core layer, intermediate core layer, outer core layer,intermediate layer, inner cover layer, intermediate cover layer, outercover layer, and the like and equivalents thereof. In one example, thepolybutadiene-based composition can be used to form a durable, cutresistant, and scuff resistant outer cover layer of a golf ball. Such anouter cover layer may constitute the entire cover of the golf ball byitself (i.e., a single layer cover) or form a multi-layer cover with oneor more inner cover layer(s) and/or intermediate cover layer(s). Thisouter cover layer can have a thickness from 0.001 inches to 0.125inches, preferably from 0.005 inches to 0.1 inches, more preferably from0.01 inches to 0.05 inches, most preferably from 0.015 inches to 0.04inches, like 0.035 inches. This outer cover layer may have a lowflexural modulus of 50,000 psi or less, preferably from 1,000 psi to30,000 psi, more preferably from 2,000 psi to 25,000 psi. The Shore Dhardness of this outer cover layer may be from 20 to 60, preferably from25 to 55, more preferably from 30 to 55, most preferably from 40 to 55.

In one example, a golf ball layer (e.g., core, intermediate layer)comprises: a) 100 parts by weight of a polybutadiene or a blend of twoor more different polybutadienes, preferably those with high cis contentas disclosed herein; b) a free radical initiator, in an amount of 3 phror less, preferably from 0.1 phr to 2 phr, more preferably 1 phr orless, further preferably 0.8 phr or less, even further preferably 0.5phr or less; c) an arylthiol, preferably chosen from CoPFIP, CoPCTP,CoPBTP, ZnPFTP, ZnPBTP, or a combination of two or more thereof, in anamount of 3 phr or less, preferably from 0.1 phr to 2 parts or less,more preferably 1.1 phr or less; optionally d) a crosslink co-agent,preferably a metal salt of an unsaturated carboxylic acid, such as ZDA,ZDMA, or a combination thereof, in an amount of 20 phr or more,preferably 25 phr or more, more preferably 30 phr or more, furtherpreferably 35 phr or more, like 40 phr; optionally e) a metal oxide,preferably ZnO; and optionally f) a filler, preferably baryte (BaSO4).Such a composition may form, at least in part, a golf ball core having adiameter of 1.5 inches or greater, preferably 1.54 inches or greater,more preferably 1.545 inches or greater, most preferably 1.55 inches orgreater. The core may have an Atti compression of 40 to 90, preferably45 to 85, more preferably 50 to 80, further preferably 50 to 75, evenmore preferably 50 to 65, most preferably 55 to 60; alternatively, thecompression may be 25 or less. The core may have a CoR of 0.75 orgreater, preferably 0.77 or greater, more preferably 0.79 or greater,further preferably 0.8 or greater, and most preferably 0.81 or greater.The core may comprise a center and one or more outer core layers. Theouter core layer may have a thickness of 0.5 inches or less, preferably0.3 inches or less, more preferably 0.25 inches to 0.3 inches.

The materials used in forming either the golf ball center or any portionof the core may be combined to form a mixture by any type of mixingknown to one of ordinary skill in the art. Suitable types of mixinginclude single pass and multi-pass mixing. Suitable mixing equipment iswell known to those of ordinary skill in the art, and such equipment mayinclude a Banbury mixer, a two-roll mill, or a twin screw extruder.Conventional mixing speeds for combining polymers are typically used.The mixing temperature depends upon the type of polymer components, andmore importantly, on the type of free-radical initiator. Suitable mixingspeeds and temperatures are well-known to those of ordinary skill in theart, or may be readily determined without undue experimentation.

The mixture can be subjected to, e.g., a compression or injectionmolding process, to obtain solid spheres for the center or hemisphericalshells for forming an intermediate layer. The temperature and durationof the molding cycle are selected based upon reactivity of the mixture.The molding cycle may have a single step of molding the mixture at asingle temperature for a predetermined time period. The molding cyclemay also include a two-step process, in which the polymer mixture isheld in the mold at an initial temperature for an initial period oftime, followed by holding at a second, typically higher temperature fora second period of time. In one example, a single-step cure cycle isemployed. The materials used in forming either the golf ball center orany portion of the core may be combined to form a golf ball by aninjection molding process, which is also well-known to one of ordinaryskill in the art. Although the curing time depends on the variousmaterials selected, those of ordinary skill in the art will be readilyable to adjust the curing time upward or downward based on theparticular materials used and the discussion herein.

The cover typically has a thickness to provide sufficient strength, goodperformance characteristics, and durability. The cover preferably has athickness of less than about 0.1 inches, more preferably, less thanabout 0.05 inches, and most preferably, between about 0.02 inches andabout 0.04 inches. A preferred construction of a multilayer golf ballcomprises a core, an inner cover layer, and an outer cover layer.Preferably, at least one of the inner and outer cover layers has athickness of less than about 0.05 inches, more preferably between about0.02 inches and about 0.04 inches, most preferably about 0.03 inches.

Inner cover layer can be formed from a hard, high flexural modulus,resilient material which contributes to the low spin, distancecharacteristics when they are struck for long shots (e.g. driver or longirons). The inner cover layer materials can have a Shore D hardness of65-80, preferably 69-74, more preferably 70-72. The flexural modulus ofinner cover layer can be at least 65,000 psi, preferably from 70,000 psito 120,000 psi, more preferably from 75,000 psi to 100,000 psi. Thethickness of the inner cover layer may be from 0.020 inches to 0.045inches, preferably from 0.030 inches to 0.040 inches.

Outer cover layer can be formed from a relatively soft thermosetmaterial in order to replicate the soft feel and high spin playcharacteristics of a balata ball for “short game” shots. The outer coverlayer can have Shore D hardness of less than 65, preferably 30-60, morepreferably 35-50, most preferably 40-45. Additionally, the materials ofthe outer cover layer can have a degree of abrasion resistance in orderto be suitable for use as a golf ball cover. The outer cover layer ofthe present disclosure can comprise any suitable thermoset material,which can be formed from a castable reactive liquid material. Thematerials for the outer cover layer include, but are not limited to,thermoset urethanes and polyurethanes, thermoset urethane ionomers,thermoset urethane epoxies, and polyureas.

When the golf ball includes an inner cover layer, this layer can includeany materials known to those of ordinary skill in the art, includingthermoplastic and thermosetting material, such as ionic copolymers orterpolymers of ethylene and methacrylic acid or acrylic acid partiallyor fully neutralized, having cations of zinc, sodium, lithium,magnesium, potassium, calcium, manganese, nickel or the like. The golfball can likewise include one or more homopolymeric or copolymeric innercover materials, such as:

(1) Vinyl resins, such as those formed by the polymerization of vinylchloride, or by the copolymerization of vinyl chloride with vinylacetate, acrylic esters or vinylidene chloride;

(2) Polyolefins, such as polyethylene, polypropylene, polybutylene andcopolymers such as ethylene methylacrylate, ethylene ethylacrylate,ethylene vinyl acetate, ethylene methacrylic or ethylene acrylic acid orpropylene acrylic acid and copolymers and homopolymers produced using asingle-site catalyst or a metallocene catalyst;

(3) Polyurethanes and polyureas, such as those prepared from polyols orpolyamines and diisocyanates or polyisocyanates;

(4) Polyamides, such as poly(hexamethylene adipamide) and othersprepared from diamines and dibasic acids, as well as those from aminoacids such as poly(caprolactam), and blends of polyamides with SURLYN,polyethylene, ethylene copolymers, ethyl-propylene-non-conjugated dieneterpolymer, and the like;

(5) Acrylic resins and blends of these resins with poly vinyl chloride,elastomers, and the like;

(6) Thermoplastics, such as urethanes; olefinic thermoplastic rubbers,such as blends of polyolefins with ethylene-propylene-non-conjugateddiene terpolymer; block copolymers of styrene and butadiene, isoprene orethylene-butylene rubber; or copoly(ether-amide), such as PEBAX, sold byELF Atochem of Philadelphia, Pa.;

(7) Polyphenylene oxide resins or blends of polyphenylene oxide withhigh impact polystyrene as sold under the trademark NORYL by GeneralElectric Company of Pittsfield, Mass.;

(8) Thermoplastic polyesters, such as polyethylene terephthalate,polybutylene terephthalate, polyethylene terephthalate/glycol modifiedand elastomers sold under the trademarks HYTREL by E.I. DuPont deNemours & Co. of Wilmington, DE, and LOMOD by General Electric Companyof Pittsfield, Mass.;

(9) Blends and alloys, including polycarbonate with acrylonitrilebutadiene styrene, polybutylene terephthalate, polyethyleneterephthalate, styrene maleic anhydride, polyethylene, elastomers, andthe like, and polyvinyl chloride with acrylonitrile butadiene styrene orethylene vinyl acetate or other elastomers; and

(10) Blends of thermoplastic rubbers with polyethylene, propylene,polyacetal, nylon, polyesters, cellulose esters, and the like.

Preferably, the inner cover includes polymers, such as ethylene,propylene, butene-1 or hexane-1 based homopolymers or copolymersincluding functional monomers, such as acrylic and methacrylic acid andfully or partially neutralized ionomer resins and their blends, methyl(meth)acrylate homopolymers and copolymers, imidized and amino groupcontaining polymers, polycarbonate, reinforced polyamides, polyphenyleneoxide, high impact polystyrene, polyether ketone, polysulfone,poly(phenylene sulfide), acrylonitrile-butadiene,acrylic-styrene-acrylonitrile, poly(ethylene terephthalate),poly(butylene terephthalate), poly(ethelyne vinyl alcohol),poly(tetrafluoroethylene) and their copolymers including functionalcomonomers, and blends thereof. Suitable inner cover compositions alsoinclude thermoplastic or thermoset polyurethanes, and thermoplastic orthermoset polyureas, such as those described in co-owned and co-pendingU.S. application Ser. No. 10/859,537, now U.S. Publication No.2005/0004325, the entire disclosure of which is incorporated herein byreference.

To prevent or minimize the penetration of moisture, typically watervapor, into core of golf ball, an intermediate moisture vapor barrierlayer may also be disposed around core. The moisture vapor barrier layerpreferably has a moisture vapor transmission rate that is lower thanthat of the cover, and more preferably less than the moisture vaportransmission rate of an ionomer resin such as Surlyn®, which is in therange of about 0.45 to about 0.95 (g·mm)/(m²·day). The moisture vaportransmission rate is defined as the mass of moisture vapor that diffusesthrough a material of a given thickness per unit area per unit time. Thepreferred standards of measuring the moisture vapor transmission rateinclude ASTM F1249-90 entitled “Standard Test Method for Water VaporTransmission Rate Through Plastic Film and Sheeting Using a ModulatedInfrared Sensor,” and ASTM F372-99 entitled “Standard Test Method forWater Vapor Transmission Rate of Flexible Barrier Materials Using anInfrared Detection Technique,” among others. The moisture vapor barrierlayer can be formed from any materials and compositions disclosed hereinthat meets the desired vapor transmission rate. Other suitablecompositions for the moisture vapor barrier layer further include thosedescribed in co-owned and co-pending U.S. application Ser. No.10/611,833, now U.S. Publication No. 2004/0048688, the entire disclosureof which is incorporated herein by reference.

Any of the inner or outer cover layers may also be formed from polymerscontaining (α,β-unsaturated carboxylic acid groups, or ionic derivativesthereof, that have been blended with organic fatty acids or saltsthereof and a suitable cation source. The acid moieties of thehighly-neutralized polymers (“HNP”), typically ethylene-based ionomers,are preferably neutralized greater than about 70%, more preferablygreater than about 90%, and most preferably at least about 100%. TheHNP's can be also be blended with a second polymer component, which, ifcontaining an acid group, may be neutralized in a conventional manner,or by the salts of organic fatty acids of the present invention, orboth. The second polymer component, which may be partially or fullyneutralized, preferably comprises ionomeric copolymers and terpolymers,ionomer precursors, thermoplastics, polyamides, polycarbonates,polyesters, polyurethanes, polyureas, thermoplastic elastomers,polybutadiene rubber, balata, metallocene-catalyzed polymers (graftedand non-grafted), single-site polymers, high-crystalline acid polymers,cationic ionomers, and the like.

The acid copolymers and ionomers thereof can be described as E/X/Ycopolymers where E is ethylene, X is an α,β-ethylenically unsaturatedcarboxylic acid, and Y is a softening comonomer. For example, X isacrylic or methacrylic acid and Y is a C₁₋₈ alkyl acrylate ormethacrylate ester. X is present in an amount of greater than 0 to 50%by weight of the polymer, preferably from 1 % to 35%, more preferablyfrom 5% to 30%, further preferably from 10% to 20%, althernatively from5% to 15%. Y is present in an amount from about 0 to 50% by weight ofthe polymer, more preferably from 5% to 45%, further preferably from 8%to 35%, even further preferably from 5% to 25%, most preferably from 10%to 20%, alternatively from 17% to 40%, like from 24% to 35%.

The organic fatty acids are aliphatic, mono-functional (saturated,unsaturated, or multi-unsaturated) organic fatty acids. Salts of theseorganic fatty acids may also be employed. The salts of organic fattyacids include barium, lithium, sodium, zinc, bismuth, chromium, cobalt,copper, potassium, strontium, titanium, tungsten, magnesium, cesium,iron, nickel, silver, aluminum, tin, or calcium, salts of fatty acidslike stearic acid, behenic acid, erucic acid, oleic acid, linoelic acid,caproic acid, caprylic acid, capric acid, lauric acid, or dimerizedderivatives thereof. It is preferred that the organic fatty acids andsalts thereof are relatively non-migratory (they do not bloom to thesurface of the polymer under ambient temperatures) and non-volatile(they do not volatilize at temperatures required for melt-blending).

The HNP may be blended with thermoplastic polymer components, such ascopolyetheresters, copolyesteresters, copolyetheramides, elastomericpolyolefins, styrene diene block copolymers and their hydrogenatedderivatives, copolyesteramides, thermoplastic polyurethanes, such ascopolyetherurethanes, copolyesterurethanes, copolyureaurethanes,epoxy-based polyurethanes, polycaprolactone-based polyurethanes,polyureas, and polycarbonate-based polyurethanes fillers, and otheringredients. The thermoplastic components can be blended in eitherbefore, during, or after the acid moieties are neutralized. Examples ofthese materials are disclosed in U.S. Patent Application PublicationNos. 2001/0018375 and 2001/0019971, which are incorporated herein, intheir entirety, by express reference thereto.

Preferably, the melt index (MI) of the base ionomer resin is 20 dg/minor greater, more preferably 40 dg/min or greater, further preferably 75dg/min or greater, most preferably 150 dg/min or greater. Particularexamples of soft and resilient ionomers include partially neutralizedethylene/(meth)acrylic acid tbutyl (meth)acrylate copolymers having anMI and level of neutralization that results in a melt processiblepolymer that has useful physical properties. The copolymers may beneutralized by one or more alkali metal, transition metal, or alkalineearth metal cations. Cations comprise lithium, sodium, potassium,magnesium, calcium, barium, or zinc, or a combination of such cations.Preferably, an amount of cation source in excess of the amount requiredto neutralize 100% of all the acid moieties in the ionomer blend isused.

The organic fatty acids or salts thereof are added in an amountsufficient to enhance the resilience of the copolymer. Preferably, theorganic fatty acids or salts thereof are added in an amount sufficientto substantially remove remaining ethylene crystallinity of thecopolymer. Preferably, the fatty organic acids or salts are added in anamount of at least about 5% by weight of the total amount of copolymerand organic acid(s). More preferably, the organic fatty acids or saltsthereof are added in an amount of at least about 15%, even morepreferably at least about 20%. Preferably, the organic fatty acid(s) areadded in an amount up to about 50% by weight of the total amount ofcopolymer and organic fatty acid(s). More preferably, the organic fattyacids or salts thereof are added in an amount of up to about 40%, morepreferably, up to about 35%. The non-volatile, non-migratory organicfatty acids preferably are one or more aliphatic, mono-functional,saturated or unsaturated organic fatty acids having less than 36 carbonatoms or salts thereof.

Processes for fatty acid/fatty salt modifications are known in the art.Particularly, the modified highly-neutralized soft, resilient acidcopolymer ionomers can be produced by: (a) melt-blending (1) ethylene,α,β-ethylenically unsaturated C₃₋₈ carboxylic acid copolymer(s) ormelt-processible ionomer(s) thereof that have their crystallinitydisrupted by addition of a softening monomer or other means with (2)sufficient amount of non-volatile, non-migratory organic fatty acids tosubstantially enhance the resilience and to disrupt (preferably remove)the remaining ethylene crystallinity, and then concurrently orsubsequently (b) adding a sufficient amount of a cation source toincrease the level of neutralization of all the acid moieties (includingthose in the acid copolymer and in the organic fatty acid, if present)to 70% or greater, preferably 80% or greater, more preferably 90% orgreater, most preferably 100% or greater.

The weight ratio of X to Y in the composition is at least about 1:20.Preferably, the weight ratio of X to Y is at least about 1:15, morepreferably, at least about 1:10. Furthermore, the weight ratio of X to Yis up to about 1:1.67, more preferably up to about 1:2. Most preferably,the weight ratio of X to Y in the composition is up to about 1:2.2.Specific acid-copolymers include ethylene/(meth)acrylic acid/n-butyl(meth)acrylate, ethylene/(meth)acrylic acid/iso-butyl (meth)acrylate,ethylene/(meth)acrylic acid/methyl (meth)acrylate, andethylene/(meth)acrylic acid/ethyl (meth)acrylate terpolymers.

The optional filler may be inorganic having a density of greater thanabout 4 g/cm³, preferably greater than 5 g/cm³, and in amounts between 0to about 60% based on the total weight of the composition. Examples ofuseful fillers include zinc oxide, barium sulfate, lead silicate andtungsten carbide, as well as the other well-known fillers used in golfballs. It is preferred that the filler materials be non-reactive oralmost non-reactive and not stiffen or raise the compression nor reducethe coefficient of restitution significantly. Additional optionaladditives that are useful herein include acid copolymer wax (e.g.,Allied wax AC 143, believed to be a 16-18% acid ethylene/acrylic acidcopolymer with a number average molecular weight of 2,040), which mayassist in preventing reaction between the filler materials (e.g., ZnO)and the acid moiety in the ethylene copolymer. Other optional additivesinclude TiO₂, which is used as a whitening agent, optical brighteners,surfactants, processing aids, etc.

While the outer cover may be formed of any of the above-listedmaterials, the outer cover preferably includes a polyurethane, polyurea,or epoxy composition, generally comprising the reaction product of atleast one polyisocyanate, at least one telechelic polyahl, and at leastone curing agent. Suitable outer cover compositions includethermoplastic or thermoset polyurethanes and thermoplastic or thermosetpolyureas, such as those described in co-owned and co-pending U.S.application Ser. No. 10/859,537, now U.S. Publication No. 2005/0004325,the entire disclosure of which is incorporated herein by reference.

The resultant golf balls typically have a CoR of greater than about 0.7,preferably greater than about 0.75, more preferably greater than about0.78, most preferably about 0.8 or greater. The golf balls alsotypically have an Atti compression of at least about 40, preferably fromabout 50 to 120, and more preferably from about 60 to 100. The golfballs typically have dimple coverage greater than about 60 percent,preferably greater than about 65 percent, and more preferably greaterthan about 75 percent. The material of the outer cover layer may have amaterial hardness, as measured by ASTM-D2240, of less than about 45Shore D, preferably less than about 40 Shore D, more preferably betweenabout 25 and about 40 Shore D, and most preferably between about 30 andabout 40 Shore D. Alternatively, the material of the outer cover layermay have a material hardness of less than about 60 Shore D, preferablyless than about 55 Shore D, and more preferably between about 40 andabout 55 Shore D. The intermediate layer or inner cover layer preferablyhas a material hardness of less than about 70 Shore D, more preferablybetween about 30 and about 70 Shore D, and most preferably, betweenabout 50 and about 65 Shore D.

The core or center may have an Atti compression of less than 100,preferably 90 or less, more preferably between 40 and 80, and mostpreferably between 50 and 70. In an alternative, low compressionembodiment, the core or center may have a compression of less than 25.The overall outer diameter of the core may be 1.650 inches or less,preferably 1.620 inches or less, more preferably between 1.500 inchesand 1.620 inches, and most preferably between 1.540 inches and 1.590inches. The outer diameter of the intermediate layer or inner coverlayer of the golf balls is preferably between 1.580 inches and 1.640inches, more preferably between 1.590 inches and 1.630 inches, and mostpreferably between 1.600 inches and 1.630 inches. The diameter of thegolf ball is preferably from 1.680 inches to 1.800 inches, morepreferably from 1.680 inches to 1.760 inches, most preferably from 1.680inches to 1.740 inches.

The various additives and compositions comprising such additives asdisclosed herein may also be used in other golf equipment, inparticular, inserts for golf clubs, such as putters, irons, and woods,and in golf shoes and components thereof.

While it is apparent that the illustrative embodiments of the inventiondisclosed herein fulfill the preferred embodiments of the presentinvention, it is appreciated that numerous modifications and otherembodiments may be devised by those skilled in the art. Therefore, itwill be understood that the appended claims are intended to cover allsuch modifications and embodiments, which would come within the spiritand scope of the present invention.

1. A golf ball comprising a core and at least one layer disposed aboutthe core, wherein the core or the layer comprises a composition formedfrom a base polymer, a crosslink initiator, and at least one additiveselected from the group consisting of boranes, borates, boronates,borinates, heterocylic compounds having at least one boron atom as aring member, boron-containing organosulfides, sulfur-containingsilicocompounds, salts of such additives, and metal salts,organometallic salts, and non-metal salts of boron complexes.
 2. Thegolf ball of claim 1, wherein the additive is selected from the groupconsisting of monoorgano-, diorgano-, and triorgano-borane compounds ofor containing BR₃, boric acids, sulfur-substituted borates, amine borateesters, boronic acids, diboronates, borinic acids, dioxaborolanes,dioxaborinanes, compounds having the structures of B(OR)₃, B(OR″)₃N,R′B(OR)₂, YR″B(OR)₂, Y′[R″B(OR)₂]₂), R′₂B(OR), and S_(y)[(R″)_(z)G]₂,metal and non-metal salts of such additives, salts containingtetraorgano-borane anions R₄B^(⊖), where R and R′ are the same ordifferent monovalent radicals selected from the group consisting of Hand organic radicals having 40 or less carbon atoms, optionally havingone or more heteroatoms, optionally substituted with one or moreelectron-withdrawing groups; R″ is the same or different divalentradicals selected from the group consisting of organic radicals having20 or less carbon atoms, optionally having one or more heteroatoms,optionally substituted with one or more electron-withdrawing groups; Yis selected from the group consisting of thiocyano, epoxyl, glycidyl,epithio, vinyl, allyl, amine, and AZ groups where A is oxygen or sulfuratom, and Z is selected from the group consisting of H, metal cations,organometallic cations, and non-metal organic cations; Y′ is a divalentradical of polysulfide S_(y) or polyselenium Se_(y); G is the same ordifferent Si-containing monovalent radicals; x is a whole number of 0,1, 2, or 3; y is an integer of 1 to 8; and z is 0 or
 1. 3. The golf ballof claim 1, wherein the composition further comprises at least onecomponent selected from the group consisting of metal salts ofunsaturated acids having 3 to 8 carbon atoms, fillers, fatty acids andsalts thereof.
 4. The golf ball of claim 1, wherein the core has a firstcoefficient of restitution, the golf ball has a second coefficient ofrestitution, and at least one of the first and second coefficients ofrestitution is 0.8 or greater.
 5. The golf ball of claim 1, wherein theadditive is present in an amount of 0.1 phr to 5 phr by weight of thebase polymer.
 6. The golf ball of claim 1, wherein the additive has atleast one C—O—B linkage, the carbon in the linkage being a secondary ortertiary carbon.
 7. The golf ball of claim 1, wherein the compositionfurther comprises at least one amine-based compound.
 8. The golf ball ofclaim 1, wherein the core has a diameter of 1.5 inches or greater and acompression of 45 to
 80. 9. The golf ball of claim 1, wherein the corehas a diameter of 1.5 inches or greater and a compression of 50 to 90,and comprises a center and an outer core layer.
 10. The golf ball ofclaim 1, wherein the at least one layer is an outer cover layer having athickness of 0.05 inches or less and a flexural modulus of 2,000 psi to30,000 psi.
 11. The golf ball of claim 1, wherein the golf ball furthercomprises an outer cover layer, and the at least one layer is anintermediate layer disposed between the core and the outer cover layer,each of the layers having a thickness of 0.05 inches or less.
 12. A golfball comprising a core and an outer cover layer disposed about the core,the core having a diameter of 1.53 inches or greater, wherein the corecomprises a composition formed from a base polymer, a crosslinkinitiator, and at least one additive selected from the group consistingof boranes, borates, boronates, borinates, heterocylic compounds havingat least one boron atom as a ring member, boron-containingorganosulfides, sulfur-containing silicocompounds, salts of suchadditives, and metal salts, organometallic salts, and non-metal salts ofboron complexes.
 13. The golf ball of claim 12, wherein the additive isselected from the group consisting of monoorgano-, diorgano-, andtriorgano-borane compounds of or containing BR₃, boric acids,sulfur-substituted borates, amine borate esters, boronic acids,diboronates, borinic acids, dioxaborolanes, dioxaborinanes, compoundshaving the structures of B(OR)₃, B(OR″)₃N, R′B(OR)₂, YR″B(OR)₂,Y′[R″B(OR)₂]₂), R′₂B(OR), and S_(y)[(R″)_(z)G]₂, metal and non-metalsalts of such additives, salts containing tetraorgano-borane anionsR₄B^(⊖), where R and R′ are the same or different monovalent radicalsselected from the group consisting of H and organic radicals having 40or less carbon atoms, optionally having one or more heteroatoms,optionally substituted with one or more electron-withdrawing groups; R″is the same or different divalent radicals selected from the groupconsisting of organic radicals having 20 or less carbon atoms,optionally having one or more heteroatoms, optionally substituted withone or more electron-withdrawing groups; Y is selected from the groupconsisting of thiocyano, epoxyl, glycidyl, epithio, vinyl, allyl, amine,and AZ groups where A is oxygen or sulfur atom, and Z is selected fromthe group consisting of H, metal cations, organometallic cations, andnon-metal organic cations; Y′ is a divalent radical of polysulfide S_(y)or polyselenium Se_(y); G is the same or different Si-containingmonovalent radicals; x is a whole number of 0, 1, 2, or 3; y is aninteger of 1 to 8; and z is 0 or
 1. 14. The golf ball of claim 12,wherein the core has a compression of 45-70, and the golf ball has acoefficient of restitution of 0.8 or greater.
 15. The golf ball of claim12, wherein the golf ball further comprises an intermediate layer havinga thickness of 0.05 inches or less disposed between the core and theouter cover layer.
 16. A golf ball comprising a core and an outer coverlayer disposed about the core, the core having a diameter of 1.53 inchesor greater, a first coefficient of restitution, and a first compression,the outer cover layer is formed from a polyurethane or polyurea and hasa thickness of 0.05 inches or less, wherein the core comprises a basepolymer, a crosslink initiator, and at least one additive that enhancesthe first coefficient of restitution and/or reduces the firstcompression, and wherein the additive is selected from the groupconsisting of boranes, borates, boronates, borinates, heterocyliccompounds having at least one boron atom as a ring member,boron-containing organosulfides, sulfur-containing silicocompounds,salts of such additives, and metal salts, organometallic salts, andnon-metal salts of boron complexes.
 17. The golf ball of claim 16,wherein the core has a compression of 45-70, and the golf ball has acoefficient of restitution of 0.8 or greater.
 18. The golf ball of claim16, wherein the at least one layer is an outer cover layer, and the golfball further comprises an intermediate layer having a thickness of 0.05inches or less disposed between the core and the outer cover layer.